WorldWideScience

Sample records for intermolecular vibronic coupling

  1. Vibronic coupling density and related concepts

    International Nuclear Information System (INIS)

    Sato, Tohru; Uejima, Motoyuki; Iwahara, Naoya; Haruta, Naoki; Shizu, Katsuyuki; Tanaka, Kazuyoshi

    2013-01-01

    Vibronic coupling density is derived from a general point of view as a one-electron property density. Related concepts as well as their applications are presented. Linear and nonlinear vibronic coupling density and related concepts, orbital vibronic coupling density, reduced vibronic coupling density, atomic vibronic coupling constant, and effective vibronic coupling density, illustrate the origin of vibronic couplings and enable us to design novel functional molecules or to elucidate chemical reactions. Transition dipole moment density is defined as an example of the one-electron property density. Vibronic coupling density and transition dipole moment density open a way to design light-emitting molecules with high efficiency.

  2. Quantum dynamics of a vibronically coupled linear chain using a surrogate Hamiltonian approach

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Myeong H., E-mail: myeong.lee@warwick.ac.uk; Troisi, Alessandro [Department of Chemistry and Centre for Scientific Computing, University of Warwick, Coventry CV4 7AL (United Kingdom)

    2016-06-07

    Vibronic coupling between the electronic and vibrational degrees of freedom has been reported to play an important role in charge and exciton transport in organic photovoltaic materials, molecular aggregates, and light-harvesting complexes. Explicitly accounting for effective vibrational modes rather than treating them as a thermal environment has been shown to be crucial to describe the effect of vibronic coupling. We present a methodology to study dissipative quantum dynamics of vibronically coupled systems based on a surrogate Hamiltonian approach, which is in principle not limited by Markov approximation or weak system-bath interaction, using a vibronic basis. We apply vibronic surrogate Hamiltonian method to a linear chain system and discuss how different types of relaxation process, intramolecular vibrational relaxation and intermolecular vibronic relaxation, influence population dynamics of dissipative vibronic systems.

  3. 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

  4. Vibronic coupling effect on the electron transport through molecules

    Science.gov (United States)

    Tsukada, Masaru; Mitsutake, Kunihiro

    2007-03-01

    Electron transport through molecular bridges or molecular layers connected to nano-electrodes is determined by the combination of coherent and dissipative processes, controlled by the electron-vibron coupling, transfer integrals between the molecular orbitals, applied electric field and temperature. We propose a novel theoretical approach, which combines ab initio molecular orbital method with analytical many-boson model. As a case study, the long chain model of the thiophene oligomer is solved by a variation approach. Mixed states of moderately extended molecular orbital states mediated and localised by dress of vibron cloud are found as eigen-states. All the excited states accompanied by multiple quanta of vibration can be solved, and the overall carrier transport properties including the conductance, mobility, dissipation spectra are analyzed by solving the master equation with the transition rates estimated by the golden rule. We clarify obtained in a uniform systematic way, how the transport mode changes from a dominantly coherent transport to the dissipative hopping transport.

  5. Electron-vibron coupling effects on electron transport via a single-molecule magnet

    Science.gov (United States)

    McCaskey, Alexander; Yamamoto, Yoh; Warnock, Michael; Burzurí, Enrique; van der Zant, Herre S. J.; Park, Kyungwha

    2015-03-01

    We investigate how the electron-vibron coupling influences electron transport via an anisotropic magnetic molecule, such as a single-molecule magnet (SMM) Fe4, by using a model Hamiltonian with parameter values obtained from density-functional theory (DFT). The magnetic anisotropy parameters, vibrational energies, and electron-vibron coupling strengths of the Fe4 are computed using DFT. A giant spin model is applied to the Fe4 with only two charge states, specifically a neutral state with a total spin S =5 and a singly charged state with S =9 /2 , which is consistent with our DFT result and experiments on Fe4 single-molecule transistors. In sequential electron tunneling, we find that the magnetic anisotropy gives rise to new features in the conductance peaks arising from vibrational excitations. In particular, the peak height shows a strong, unusual dependence on the direction as well as magnitude of applied B field. The magnetic anisotropy also introduces vibrational satellite peaks whose position and height are modified with the direction and magnitude of applied B field. Furthermore, when multiple vibrational modes with considerable electron-vibron coupling have energies close to one another, a low-bias current is suppressed, independently of gate voltage and applied B field, although that is not the case for a single mode with a similar electron-vibron coupling. In the former case, the conductance peaks reveal a stronger B -field dependence than in the latter case. The new features appear because the magnetic anisotropy barrier is of the same order of magnitude as the energies of vibrational modes with significant electron-vibron coupling. Our findings clearly show the interesting interplay between magnetic anisotropy and electron-vibron coupling in electron transport via the Fe4. Similar behavior can be observed in transport via other anisotropic magnetic molecules.

  6. Towards quantification of vibronic coupling in photosynthetic antenna complexes

    Energy Technology Data Exchange (ETDEWEB)

    Singh, V. P.; Westberg, M.; Wang, C.; Gellen, T.; Engel, G. S., E-mail: gsengel@uchicago.edu [Department of Chemistry, The James Franck Institute and The Institute for Biophysical Dynamics, The University of Chicago, Chicago, Illinois 60637 (United States); Dahlberg, P. D. [Graduate Program in the Biophysical Sciences, The James Franck Institute and The Institute for Biophysical Dynamics, The University of Chicago, Chicago, Illinois 60637 (United States); Gardiner, A. T.; Cogdell, R. J. [Department of Botany, Institute of Molecular Cell and Systems Biology, University of Glasgow, Glasgow, Scotland (United Kingdom)

    2015-06-07

    Photosynthetic antenna complexes harvest sunlight and efficiently transport energy to the reaction center where charge separation powers biochemical energy storage. The discovery of existence of long lived quantum coherence during energy transfer has sparked the discussion on the role of quantum coherence on the energy transfer efficiency. Early works assigned observed coherences to electronic states, and theoretical studies showed that electronic coherences could affect energy transfer efficiency—by either enhancing or suppressing transfer. However, the nature of coherences has been fiercely debated as coherences only report the energy gap between the states that generate coherence signals. Recent works have suggested that either the coherences observed in photosynthetic antenna complexes arise from vibrational wave packets on the ground state or, alternatively, coherences arise from mixed electronic and vibrational states. Understanding origin of coherences is important for designing molecules for efficient light harvesting. Here, we give a direct experimental observation from a mutant of LH2, which does not have B800 chromophores, to distinguish between electronic, vibrational, and vibronic coherence. We also present a minimal theoretical model to characterize the coherences both in the two limiting cases of purely vibrational and purely electronic coherence as well as in the intermediate, vibronic regime.

  7. Vibronic coupling in molecular crystals: A Franck-Condon Herzberg-Teller model of H-aggregate fluorescence based on quantum chemical cluster calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wykes, M., E-mail: mikewykes@gmail.com; Parambil, R.; Gierschner, J. [Madrid Institute for Advanced Studies, IMDEA Nanoscience, Calle Faraday 9, Campus Cantoblanco, 28049 Madrid (Spain); Beljonne, D. [Laboratory for Chemistry of Novel Materials, University of Mons, Place du Parc 20, 7000 Mons (Belgium)

    2015-09-21

    Here, we present a general approach to treating vibronic coupling in molecular crystals based on atomistic simulations of large clusters. Such clusters comprise model aggregates treated at the quantum chemical level embedded within a realistic environment treated at the molecular mechanics level. As we calculate ground and excited state equilibrium geometries and vibrational modes of model aggregates, our approach is able to capture effects arising from coupling to intermolecular degrees of freedom, absent from existing models relying on geometries and normal modes of single molecules. Using the geometries and vibrational modes of clusters, we are able to simulate the fluorescence spectra of aggregates for which the lowest excited state bears negligible oscillator strength (as is the case, e.g., ideal H-aggregates) by including both Franck-Condon (FC) and Herzberg-Teller (HT) vibronic transitions. The latter terms allow the adiabatic excited state of the cluster to couple with vibrations in a perturbative fashion via derivatives of the transition dipole moment along nuclear coordinates. While vibronic coupling simulations employing FC and HT terms are well established for single-molecules, to our knowledge this is the first time they are applied to molecular aggregates. Here, we apply this approach to the simulation of the low-temperature fluorescence spectrum of para-distyrylbenzene single-crystal H-aggregates and draw comparisons with coarse-grained Frenkel-Holstein approaches previously extensively applied to such systems.

  8. Electron-vibron coupling effects on electron transport via a single-molecule magnet

    NARCIS (Netherlands)

    McCaskey, A.; Yamamoto, Y.; Warnock, M.; Burzuri, E.; Van der Zant, H.S.J.; Park, K.

    2015-01-01

    We investigate how the electron-vibron coupling influences electron transport via an anisotropic magnetic molecule, such as a single-molecule magnet (SMM) Fe4, by using a model Hamiltonian with parameter values obtained from density-functional theory (DFT). The magnetic anisotropy parameters,

  9. A study of vibronic coupling in the tilde C state of CO2+

    International Nuclear Information System (INIS)

    Roy, P.; Ferrett, T.A.; Schmidt, V.; Parr, A.C.; Southworth, S.H.; Hardis, J.E.; Bartlett, R.; Trela, W.; Dehmer, J.L.

    1987-01-01

    We have studied vibronic coupling in vibrationally resolved photoionization to the fourth electronic state of CO 2 + , C( 2 Σ/sub g/ + ), in the photon-energy range h nu = 20 to 28.5 eV. The measurements utilize high-resolution hemispherical electron analyzers, equipped with area detectors, and the SURF-II synchrotron radiation source at the National Bureau of Standards. The angular distribution asymmetry-parameters (β) for the allowed C(0,0,0) and forbidden C(1,0,1) (19.747 eV binding energy) peaks are found to be quite different. However, similarities between the C(1,0,1) β curve and that for the B state suggest that vibronic coupling to the B( 2 Σ/sub u/ + ) state of CO 2 + is the explanation for the intensity of the C state forbidden band in the first 8 eV above threshold

  10. The exact wavefunction factorization of a vibronic coupling system

    International Nuclear Information System (INIS)

    Chiang, Ying-Chih; Klaiman, Shachar; Otto, Frank; Cederbaum, Lorenz S.

    2014-01-01

    We investigate the exact wavefunction as a single product of electronic and nuclear wavefunction for a model conical intersection system. Exact factorized spiky potentials and nodeless nuclear wavefunctions are found. The exact factorized potential preserves the symmetry breaking effect when the coupling mode is present. Additionally nodeless wavefunctions are found to be closely related to the adiabatic nuclear eigenfunctions. This phenomenon holds even for the regime where the non-adiabatic coupling is relevant, and sheds light on the relation between the exact wavefunction factorization and the adiabatic approximation

  11. Tunnel magnetoresistance of magnetic molecules with spin-vibron coupling

    Directory of Open Access Journals (Sweden)

    Ahmed Kenawy

    2017-05-01

    Full Text Available The effect of molecular vibrations on the tunnel magnetoresistance (TMR of a magnetic tunnel junction with a single spin-anisotropic molecule interconnecting its electrodes is investigated theoretically. We demonstrate that if these vibrations couple at the same time to the charge of tunneling electrons and to the spin of the molecule, the spin anisotropy of such a molecule becomes enhanced. This has, in turn, a profound impact on the TMR of such a device showing that molecular vibrations lead to a significant change of spin-polarized transport, differing for the parallel and antiparallel magnetic configuration of the junction.

  12. Raman dispersion spectroscopy on the highly saddled nickel(II)-octaethyltetraphenylporphyrin reveals the symmetry of nonplanar distortions and the vibronic coupling strength of normal modes

    International Nuclear Information System (INIS)

    Schweitzer-Stenner, R.; Stichternath, A.; Dreybrodt, W.; Jentzen, W.; Song, X.; Shelnutt, J.A.; Nielsen, O.F.; Medforth, C.J.; Smith, K.M.

    1997-01-01

    We have measured the polarized Raman cross sections and depolarization ratios of 16 fundamental modes of nickel octaethyltetraphenylporphyrin in a CS 2 solution for 16 fundamental modes, i.e., the A 1g -type vibrations ν 1 , ν 2 , ν 3 , ν 4 , ν 5 , and φ 8 , the B 1g vibrations ν 11 and ν 14 , the B 2g vibrations ν 28 , ν 29 , and ν 30 and the antisymmetric A 2g modes ν 19 , ν 20 , ν 22 , and ν 23 as function of the excitation wavelength. The data cover the entire resonant regions of the Q- and B-bands. They were analyzed by use of a theory which describes intra- and intermolecular coupling in terms of a time-independent nonadiabatic perturbation theory [E. Unger, U. Bobinger, W. Dreybrodt, and R. Schweitzer-Stenner, J. Phys. Chem. 97, 9956 (1993)]. This approach explicitly accounts in a self-consistent way for multimode mixing with all Raman modes investigated. The vibronic coupling parameters obtained from this procedure were then used to successfully fit the vibronic side bands of the absorption spectrum and to calculate the resonance excitation profiles in absolute units. Our results show that the porphyrin macrocycle is subject to B 2u -(saddling) and B 1u -(ruffling) distortions which lower its symmetry to S 4 . Thus, evidence is provided that the porphyrin molecule maintains the nonplanar structure of its crystal phase in an organic solvent. The vibronic coupling parameters indicate a breakdown of the four-orbital model. This notion is corroborated by (ZINDO/S) calculations which reveal that significant configurational interaction occurs between the electronic transitions into |Q right-angle- and |1B right-angle-states and various porphyrin→porphyrin, metal→porphyrin, and porphyrin→metal transitions. (Abstract Truncated)

  13. Jahn-Teller effect in Rydberg series: A multi-state vibronic coupling problem

    International Nuclear Information System (INIS)

    Staib, A.; Domcke, W.; Sobolewski, A.L.

    1990-01-01

    Two simple limiting cases of Jahn-Teller (JT) coupling in Rydberg states of polyatomic molecules are considered, namely (i) JT coupling in Rydberg orbitals as well as in the ionization continuum (nondegenerate ion core, degenerate Rydberg series) and (ii) JT coupling in the ion core (degenerate ion core, nondegenerate Rydberg series). For both models simple and efficient algorithms for the computation of spectra (dynamical JT effect) are developed. The orbital JT effect is shown to represent a novel type of multi-state vibronic coupling, giving rise to interesting spectroscopic phenomena, among them resonant inter-Rydberg perturbations and JT induced autoionization. Particular attention is paid to the demonstration of the characteristic spectroscopic signatures of the two types of JT coupling in Rydberg states. (orig.)

  14. Vibronic coupling in ionized organic molecules: structural distortions and chemical reactions

    International Nuclear Information System (INIS)

    Williams, Ffrancon

    2003-01-01

    Ionized organic molecules (radical cations) in radiation chemistry are liable to undergo vibronic coupling whenever there is a relatively small energy gap (∼0.5-1.5 eV) between their ground and excited states. As a result of this mixing, the force constant for the symmetry-allowed vibrational mode that couples these states is lowered in the ground state of the radical cation so that deformation can take place more easily along this specific mode. This pseudo-Jahn-Teller effect can then result in a permanent structural distortion of the radical cation relative to the symmetry of the parent neutral molecule. It can also bring about an energetically favored pathway for a facile chemical rearrangement along a reaction coordinate defined by the coupling mode. Examples taken from matrix-isolation studies are used to illustrate these dramatic consequences of vibronic coupling in radical cations. Thus, the bicyclo[2.2.2]oct-2-ene and tetramethylurea radical cations are found to have twisted structures departing from the C 2v symmetry of their parent molecules, while the oxirane and bicyclo[1.1.1]pentane radical cations undergo ring-opening rearrangements along reaction coordinates that correspond to the deformational modes predicted by the pseudo-Jahn-Teller effect

  15. Vibronic coupling in ionized organic molecules. Structural distortions and chemical reactions

    International Nuclear Information System (INIS)

    Williams, F.

    2002-01-01

    Complete text of publication follows. Ionized organic molecules (radical cations, RC) are prone to undergo vibronic coupling whenever there is a relatively small energy gap ( 2v point group of the neutral parent molecule by twisting at the olefinic π bond to the lower C 2 symmetry in the RC (Chem. Eur. J. 2002, 8, 1074). These experiments clearly revealed a double minimum in the potential energy surface along the a 2 torsional mode. This is in accord with the coupling of the 2 B 1 and 2 B 2 Born-Oppenheimer states in C 2v symmetry, this mixing of the 2 B 1 π-ionized ground state and the 2 B 2 δ-ionized excited state being facilitated by the low (∼ 1.0 eV) gap between these states, as estimated from photoelectron spectroscopy. Turning to the second class of RC where unimolecular rearrangement reactions are promoted by vibronic interaction, several cases have emerged where the rearrangement would not be expected if it were based only on the ground-state properties of the RC. It was found (Chem. Phy. Lett. 1988, 143, 521) that the ethylene oxide RC undergoes C-C ring opening to the oxallyl species despite the fact that the ground state corresponds to ionization from the nonbonding oxygen π lone-pair orbital. The reaction develops excited-state character as a result of the vibronic mixing so that the activation barrier to ring opening is lowered. We will discuss the unusual rearrangements of the bicyclo[1.1.1.]pentane and [1.1.1]propellane RC from a similar perspective, emphasis being placed on the decisive role of symmetry in predicting the course of these rearrangements. We illustrate how this approach can reconcile conflicting considerations on some of the 'unexpected' reaction pathways followed by highly strained organic RC

  16. Vibronic coupling in asymmetric bichromophores: Experimental investigation of diphenylmethane-d5

    International Nuclear Information System (INIS)

    Pillsbury, Nathan R.; Kidwell, Nathanael M.; Nebgen, Benjamin; Slipchenko, Lyudmila V.; Zwier, Timothy S.; Douglass, Kevin O.; Plusquellic, David F.; Cable, John R.

    2014-01-01

    Vibrationally and rotationally resolved electronic spectra of diphenylmethane-d 5 (DPM-d 5 ) are reported in the isolated-molecule environment of a supersonic expansion. While small, the asymmetry induced by deuteration of one of the aromatic rings is sufficient to cause several important effects that change the principle mechanism of vibronic coupling between the close-lying S 1 and S 2 states, and spectroscopic signatures such coupling produces. The splitting between S 1 and S 2 origins is 186 cm −1 , about 50% greater than its value in DPM-d 0 (123 cm −1 ), and an amount sufficient to bring the S 2 zero-point level into near-resonance with the v = 1 level in the S 1 state of a low-frequency phenyl flapping mode, ν R = 191 cm −1 . Dispersed fluorescence spectra bear clear evidence that Δv(R) = 1 Herzberg-Teller coupling dominates the near-resonant internal mixing between the S 1 and S 2 manifolds. The fluorescence into each pair of Franck-Condon active ring modes shows an asymmetry that suggests incorrectly that the S 1 and S 2 states may be electronically localized. From rotationally resolved studies, the S 0 and S 1 states have been well-fit to asymmetric rotor Hamiltonians while the S 2 state is perturbed and not fit. The transition dipole moment (TDM) orientation of the S 1 state is nearly perpendicular to the C 2 symmetry axes with 66(2)%:3(1)%:34(2)% a:b:c hybrid-type character while that of the S 2 origin contains 50(10)% a:c-type (S 1 ) and 50(10)% b-type (S 2 ) character. A model is put forward that explains qualitatively the TDM compositions and dispersed emission patterns without the need to invoke electronic localization. The experimental data discussed here serve as a foundation for a multi-mode vibronic coupling model capable of being applied to asymmetric bichromophores, as presented in the work of B. Nebgen and L. V. Slipchenko [“Vibronic coupling in asymmetric bichromophores: Theory and application to diphenylmethane-d 5 ,” J. Chem

  17. Vibronic coupling in asymmetric bichromophores: Experimental investigation of diphenylmethane-d{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Pillsbury, Nathan R.; Kidwell, Nathanael M.; Nebgen, Benjamin; Slipchenko, Lyudmila V.; Zwier, Timothy S., E-mail: david.plusquellic@nist.gov, E-mail: zwier@purdue.edu [Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084 (United States); Douglass, Kevin O.; Plusquellic, David F., E-mail: david.plusquellic@nist.gov, E-mail: zwier@purdue.edu [Quantum Electronics and Photonics Division, Physical Measurement Laboratory, National Institute of Standards and Technology, Boulder, Colorado 80305-3328 (United States); Cable, John R. [Department of Chemistry and Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403-0213 (United States)

    2014-08-14

    Vibrationally and rotationally resolved electronic spectra of diphenylmethane-d{sub 5} (DPM-d{sub 5}) are reported in the isolated-molecule environment of a supersonic expansion. While small, the asymmetry induced by deuteration of one of the aromatic rings is sufficient to cause several important effects that change the principle mechanism of vibronic coupling between the close-lying S{sub 1} and S{sub 2} states, and spectroscopic signatures such coupling produces. The splitting between S{sub 1} and S{sub 2} origins is 186 cm{sup −1}, about 50% greater than its value in DPM-d{sub 0} (123 cm{sup −1}), and an amount sufficient to bring the S{sub 2} zero-point level into near-resonance with the v = 1 level in the S{sub 1} state of a low-frequency phenyl flapping mode, ν{sub R} = 191 cm{sup −1}. Dispersed fluorescence spectra bear clear evidence that Δv(R) = 1 Herzberg-Teller coupling dominates the near-resonant internal mixing between the S{sub 1} and S{sub 2} manifolds. The fluorescence into each pair of Franck-Condon active ring modes shows an asymmetry that suggests incorrectly that the S{sub 1} and S{sub 2} states may be electronically localized. From rotationally resolved studies, the S{sub 0} and S{sub 1} states have been well-fit to asymmetric rotor Hamiltonians while the S{sub 2} state is perturbed and not fit. The transition dipole moment (TDM) orientation of the S{sub 1} state is nearly perpendicular to the C{sub 2} symmetry axes with 66(2)%:3(1)%:34(2)% a:b:c hybrid-type character while that of the S{sub 2} origin contains 50(10)% a:c-type (S{sub 1}) and 50(10)% b-type (S{sub 2}) character. A model is put forward that explains qualitatively the TDM compositions and dispersed emission patterns without the need to invoke electronic localization. The experimental data discussed here serve as a foundation for a multi-mode vibronic coupling model capable of being applied to asymmetric bichromophores, as presented in the work of B. Nebgen and L. V

  18. Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences

    NARCIS (Netherlands)

    Halpin, Alexei; Johnson, Philip J. M.; Tempelaar, Roel; Murphy, R. Scott; Knoester, Jasper; Jansen, Thomas L. C.; Miller, R. J. Dwayne

    The observation of persistent oscillatory signals in multidimensional spectra of protein-pigment complexes has spurred a debate on the role of coherence-assisted electronic energy transfer as a key operating principle in photosynthesis. Vibronic coupling has recently been proposed as an explanation

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-05-28

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

  20. Carotenoid-to-bacteriochlorophyll energy transfer through vibronic coupling in LH2 from Phaeosprillum molischianum.

    Science.gov (United States)

    Thyrhaug, Erling; Lincoln, Craig N; Branchi, Federico; Cerullo, Giulio; Perlík, Václav; Šanda, František; Lokstein, Heiko; Hauer, Jürgen

    2018-03-01

    The peripheral light-harvesting antenna complex (LH2) of purple photosynthetic bacteria is an ideal testing ground for models of structure-function relationships due to its well-determined molecular structure and ultrafast energy deactivation. It has been the target for numerous studies in both theory and ultrafast spectroscopy; nevertheless, certain aspects of the convoluted relaxation network of LH2 lack a satisfactory explanation by conventional theories. For example, the initial carotenoid-to-bacteriochlorophyll energy transfer step necessary on visible light excitation was long considered to follow the Förster mechanism, even though transfer times as short as 40 femtoseconds (fs) have been observed. Such transfer times are hard to accommodate by Förster theory, as the moderate coupling strengths found in LH2 suggest much slower transfer within this framework. In this study, we investigate LH2 from Phaeospirillum (Ph.) molischianum in two types of transient absorption experiments-with narrowband pump and white-light probe resulting in 100 fs time resolution, and with degenerate broadband 10 fs pump and probe pulses. With regard to the split Q x band in this system, we show that vibronically mediated transfer explains both the ultrafast carotenoid-to-B850 transfer, and the almost complete lack of transfer to B800. These results are beyond Förster theory, which predicts an almost equal partition between the two channels.

  1. 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.

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

    KAUST Repository

    Li, Wenjun; Ajitha, Manjaly John; Lang, Ming; Huang, Kuo-Wei; Wang, Jian

    2017-01-01

    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

  3. Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

    Energy Technology Data Exchange (ETDEWEB)

    Perlík, Václav; Seibt, Joachim; Šanda, František; Mančal, Tomáš [Institute of Physics, Faculty of Mathematics and Physics, Charles University in Prague, Ke Karlovu 5, Prague 121 16 (Czech Republic); Cranston, Laura J.; Cogdell, Richard J. [Institute of Molecular Cell and System Biology, College of Medical, Veterinary and Life Sciences, University of Glasgow, Glasgow Biomedical Research Centre, 120 University Place, Glasgow G12 8TA, Scotland (United Kingdom); Lincoln, Craig N.; Hauer, Jürgen, E-mail: juergen.hauer@tuwien.ac.at [Photonics Institute, Vienna University of Technology, Gusshausstrasse 27, 1040 Vienna (Austria); Savolainen, Janne [Department of Physical Chemistry II, Ruhr-University Bochum, 44780 Bochum (Germany)

    2015-06-07

    The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system’s Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems.

  4. Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

    International Nuclear Information System (INIS)

    Perlík, Václav; Seibt, Joachim; Šanda, František; Mančal, Tomáš; Cranston, Laura J.; Cogdell, Richard J.; Lincoln, Craig N.; Hauer, Jürgen; Savolainen, Janne

    2015-01-01

    The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system’s Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems

  5. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.

    Science.gov (United States)

    Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-11-21

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  6. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

    International Nuclear Information System (INIS)

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-01-01

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  7. The coherence lifetime-borrowing effect in vibronically coupled molecular aggregates under non-perturbative system-environment interactions.

    Science.gov (United States)

    Yeh, Shu-Hao; Engel, Gregory S.; Kais, Sabre

    Recently it has been suggested that the long-lived coherences in some photosynthetic pigment-protein systems, such as the Fenna-Matthews-Olson complex, could be attributed to the mixing of the pigments' electronic and vibrational degrees of freedom. In order to verify whether this is the case and to understand its underlying mechanism, a theoretical model capable of including both the electronic excitations and intramolecular vibrational modes of the pigments is necessary. Our model simultaneously considers the electronic and vibrational degrees of freedom, treating the system-environment interactions non-perturbatively by implementing the hierarchical equations of motion approach. Here we report the simulated two-dimensional electronic spectra of vibronically coupled molecular dimers to demonstrate how the electronic coherence lifetimes can be extended by borrowing the lifetime from the vibrational coherences. Funded by Qatar National Research Fund and Qatar Environment and Energy Research Institute.

  8. 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.

  9. Chemical origin of blue- and redshifted hydrogen bonds: intramolecular hyperconjugation and its coupling with intermolecular hyperconjugation.

    Science.gov (United States)

    Li, An Yong

    2007-04-21

    Upon formation of a H bond Y...H-XZ, intramolecular hyperconjugation n(Z)-->sigma*(X-H) of the proton donor plays a key role in red- and blueshift characters of H bonds and must be introduced in the concepts of hyperconjugation and rehybridization. Intermolecular hyperconjugation transfers electron density from Y to sigma*(X-H) and causes elongation and stretch frequency redshift of the X-H bond; intramolecular hyperconjugation couples with intermolecular hyperconjugation and can adjust electron density in sigma*(X-H); rehybridization causes contraction and stretch frequency blueshift of the X-H bond on complexation. The three factors--intra- and intermolecular hyperconjugations and rehybridization--determine commonly red- or blueshift of the formed H bond. A proton donor that has strong intramolecular hyperconjugation often forms blueshifted H bonds.

  10. Geometric phase effects in low-energy dynamics near conical intersections: A study of the multidimensional linear vibronic coupling model

    International Nuclear Information System (INIS)

    Joubert-Doriol, Loïc; Ryabinkin, Ilya G.; Izmaylov, Artur F.

    2013-01-01

    In molecular systems containing conical intersections (CIs), a nontrivial geometric phase (GP) appears in the nuclear and electronic wave functions in the adiabatic representation. We study GP effects in nuclear dynamics of an N-dimensional linear vibronic coupling (LVC) model. The main impact of GP on low-energy nuclear dynamics is reduction of population transfer between the local minima of the LVC lower energy surface. For the LVC model, we proposed an isometric coordinate transformation that confines non-adiabatic effects within a two-dimensional subsystem interacting with an N − 2 dimensional environment. Since environmental modes do not couple electronic states, all GP effects originate from nuclear dynamics within the subsystem. We explored when the GP affects nuclear dynamics of the isolated subsystem, and how the subsystem-environment interaction can interfere with GP effects. Comparing quantum dynamics with and without GP allowed us to devise simple rules to determine significance of the GP for nuclear dynamics in this model

  11. Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

    Directory of Open Access Journals (Sweden)

    Jungho Jun

    2013-08-01

    Full Text Available Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion–dipole pair.

  12. Geometric phase effects in excited state dynamics through a conical intersection in large molecules: N-dimensional linear vibronic coupling model study

    Science.gov (United States)

    Li, Jiaru; Joubert-Doriol, Loïc; Izmaylov, Artur F.

    2017-08-01

    We investigate geometric phase (GP) effects in nonadiabatic transitions through a conical intersection (CI) in an N-dimensional linear vibronic coupling (ND-LVC) model. This model allows for the coordinate transformation encompassing all nonadiabatic effects within a two-dimensional (2D) subsystem, while the other N - 2 dimensions form a system of uncoupled harmonic oscillators identical for both electronic states and coupled bi-linearly with the subsystem coordinates. The 2D subsystem governs ultra-fast nonadiabatic dynamics through the CI and provides a convenient model for studying GP effects. Parameters of the original ND-LVC model define the Hamiltonian of the transformed 2D subsystem and thus influence GP effects directly. Our analysis reveals what values of ND-LVC parameters can introduce symmetry breaking in the 2D subsystem that diminishes GP effects.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-28

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

  14. Strong Intermolecular Exciton Couplings in Solid-State Circular Dichroism of Aryl Benzyl Sulfoxides

    Czech Academy of Sciences Publication Activity Database

    Padula, Daniele; Di Pietro, S.; Capozzi, M. A. M.; Cardellicchio, C.; Pescitelli, G.

    2014-01-01

    Roč. 26, č. 9 (2014), s. 462-470 ISSN 0899-0042 Institutional support: RVO:61388963 Keywords : organic crystals * TDDFT CD calculations * pairwise additive approximation * two-body effects * intermolecular forces in crystal lattices Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.886, year: 2014

  15. Evaluation of coupling terms between intra- and intermolecular vibrations in coarse-grained normal-mode analysis: Does a stronger acid make a stiffer hydrogen bond?

    Science.gov (United States)

    Houjou, Hirohiko

    2011-10-01

    Using theory of harmonic normal-mode vibration analysis, we developed a procedure for evaluating the anisotropic stiffness of intermolecular forces. Our scheme for coarse-graining of molecular motions is modified so as to account for intramolecular vibrations in addition to relative translational/rotational displacement. We applied this new analytical scheme to four carboxylic acid dimers, for which coupling between intra- and intermolecular vibrations is crucial for determining the apparent stiffness of the intermolecular double hydrogen bond. The apparent stiffness constant was analyzed on the basis of a conjunct spring model, which defines contributions from true intermolecular stiffness and molecular internal stiffness. Consequently, the true intermolecular stiffness was in the range of 43-48 N m-1 for all carboxylic acids studied, regardless of the molecules' acidity. We concluded that the difference in the apparent stiffness can be attributed to differences in the internal stiffness of the respective molecules.

  16. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    Energy Technology Data Exchange (ETDEWEB)

    Haverkate, Lucas A.; Mulder, Fokko M. [Reactor Institute Delft, Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, 2629JB Delft (Netherlands); Zbiri, Mohamed, E-mail: zbiri@ill.fr; Johnson, Mark R. [Institut Laue Langevin, 38042 Grenoble Cedex 9 (France); Carter, Elizabeth [Vibrational Spectroscopy Facility, School of Chemistry, The University of Sydney, NSW 2008 (Australia); Kotlewski, Arek; Picken, S. [ChemE-NSM, Faculty of Chemistry, Delft University of Technology, 2628BL/136 Delft (Netherlands); Kearley, Gordon J. [Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW 2234 (Australia)

    2014-01-07

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10{sup −2} electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

  17. Analysis of vibronic interactions in the molecules of cross-conjugated ketones

    Directory of Open Access Journals (Sweden)

    Kompaneez V.V.

    2017-01-01

    Full Text Available We have done quantitative analysis of vibronic parameters of two cross-conjugated δ-dimethylaminoketones. The research shows the influence of С-N and C=O bonds in the rings, and the radicals with nitro compounds on the vibronic parameters of characteristic bands, which describe the state (vibrations, types of deformation under excitation of the phenyl ring and the polyene bridge. Results described impact of the substituent’s nature on the parameters of intra- and intermolecular interactions presents for the studied compounds.

  18. Intermolecular interactions

    International Nuclear Information System (INIS)

    Kaplan, I.G.; Rodimova, O.B.; AN SSSR, Tomsk. Inst. Optiki Atmosfery)

    1978-01-01

    The present state of the intermolecular interaction theory is described. The general physical picture of the molecular interactions is given, the relative contributions of interactions of different types are analyzed (electrostatic, resonance, induction, dispersion, relativistic, magnetostatic and exchange), and the main ones in each range of separations are picked out. The methods of the potential curve calculations are considered, specific for definite separations between the interacting systems. The special attention is paid to the analysis of approximations used in different theoretical calculation methods

  19. Reassigning the CaH+ 11Σ → 21Σ vibronic transition with CaD+

    Science.gov (United States)

    Condoluci, J.; Janardan, S.; Calvin, A. T.; Rugango, R.; Shu, G.; Sherrill, C. D.; Brown, K. R.

    2017-12-01

    We observe vibronic transitions in CaD+ between the 11Σ and 21Σ electronic states by resonance enhanced multiphoton photodissociation spectroscopy in a Coulomb crystal. The vibronic transitions are compared with previous measurements on CaH+. The result is a revised assignment of the CaH+ vibronic levels and a disagreement with multi-state-complete-active-space second-order perturbation theory theoretical calculations by approximately 700 cm-1. Updated high-level coupled-cluster calculations that include core-valence correlations reduce the disagreement between theory and experiment to 300 cm-1.

  20. Modeling the effect of intermolecular force on the size-dependent pull-in behavior of beam-type NEMS using modified couple stress theory

    Energy Technology Data Exchange (ETDEWEB)

    Beni, Yaghoub Tadi; Karimipour, Iman [Shahrekord University, Shahrekord (Iran, Islamic Republic of); Abadyan, Mohamadreza [Islamic Azad University, Shahrekord (Iran, Islamic Republic of)

    2014-09-15

    Experimental observations reveal that the physical response of nano structures is size-dependent. Herein, modified couple stress theory has been used to study the effect of intermolecular van der Waals force on the size dependent pull-in of nano bridges and nano cantilevers. Three approaches including using differential transformation method, applying numerical method and developing a simple lumped parameter model have been employed to solve the governing equation of the systems. The pull-in parameters i.e. critical tip deflection and instability voltage of the nano structures have been determined. Effect of the van der Waals attraction and the size dependency and the importance of coupling between them on the pull-in performance have been discussed.

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

    Directory of Open Access Journals (Sweden)

    Claudio N. Cavasotto

    2003-04-01

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

  2. Modeling the effect of intermolecular force on the size-dependent pull-in behavior of beam-type NEMS using modified couple stress theory

    International Nuclear Information System (INIS)

    Beni, Yaghoub Tadi; Karimipour, Iman; Abadyan, Mohamadreza

    2014-01-01

    Experimental observations reveal that the physical response of nano structures is size-dependent. Herein, modified couple stress theory has been used to study the effect of intermolecular van der Waals force on the size dependent pull-in of nano bridges and nano cantilevers. Three approaches including using differential transformation method, applying numerical method and developing a simple lumped parameter model have been employed to solve the governing equation of the systems. The pull-in parameters i.e. critical tip deflection and instability voltage of the nano structures have been determined. Effect of the van der Waals attraction and the size dependency and the importance of coupling between them on the pull-in performance have been discussed.

  3. Intermolecular spectroscopy

    International Nuclear Information System (INIS)

    Gelbart, W.M.

    1980-01-01

    In this article some of the theoretical background is presented for the following papers on 'Intermolecular Spectroscopy and Dynamical Properties of Dense Systems'. In Section 1 we outline a simple semi-classical description of the interaction between optical radiation and matter. The motion of a many-body polarizability is introduced; limiting forms of this complicated quantity lead to the familiar cases of light scattering spectra. In Section 2 we consider the linear response approximation, and the equation of motion for the many-body density matrix is solved to first order in the matter-radiation interaction. The often quoted fluctuation-dissipation theorem and the time-dependent, equilibrium correlation functions are discussed. Section 3 treats the problem of the local field. In Section 4 we consider the special case of collision-induced light scattering by atomic fluids in the low-density limit. This allows us to focus on determining the interaction polarizability for simple gases. Finally, in Section 5 we distinguish between collision-induced and multiple light scattering, and discuss the double-light-scattering analyses which provide new information about critical and thermodynamically unstable fluids. (KBE)

  4. Rabi-vibronic resonance with large number of vibrational quanta

    OpenAIRE

    Glenn, R.; Raikh, M. E.

    2011-01-01

    We study theoretically the Rabi oscillations of a resonantly driven two-level system linearly coupled to a harmonic oscillator (vibrational mode) with frequency, \\omega_0. We show that for weak coupling, \\omega_p \\ll \\omega_0, where \\omega_p is the polaronic shift, Rabi oscillations are strongly modified in the vicinity of the Rabi-vibronic resonance \\Omega_R = \\omega_0, where \\Omega_R is the Rabi frequency. The width of the resonance is (\\Omega_R-\\omega_0) \\sim \\omega_p^{2/3} \\omega_0^{1/3} ...

  5. Multi-State Vibronic Interactions in Fluorinated Benzene Radical Cations.

    Science.gov (United States)

    Faraji, S.; Köppel, H.

    2009-06-01

    Conical intersections of potential energy surfaces have emerged as paradigms for signalling strong nonadiabatic coupling effects. An important class of systems where some of these effects have been analyzed in the literature, are the benzene and benzenoid cations, where the electronic structure, spectroscopy, and dynamics have received great attention in the literature. In the present work a brief overview is given over our theoretical treatments of multi-mode and multi-state vibronic interactions in the benzene radical cation and some of its fluorinated derivatives. The fluorobenzene derivatives are of systematic interest for at least two different reasons. (1) The reduction of symmetry by incomplete fluorination leads to a disappearance of the Jahn-Teller effect present in the parent cation. (2) A specific, more chemical effect of fluorination consists in the energetic increase of the lowest σ-type electronic states of the radical cations. The multi-mode multi-state vibronic interactions between the five lowest electronic states of the fluorobenzene radical cations are investigated theoretically, based on ab initio electronic structure data, and employing the well-established linear vibronic coupling model, augmented by quadratic coupling terms for the totally symmetric vibrational modes. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of tilde{X}-tilde{A} and tilde{B}-tilde{C}-tilde{D} cationic states, while the interactions between these two sets of states are found to be weaker and depend on the particular isomer. This is attributed to the different location of the minima of the various conical intersections occurring in these systems. Wave-packet dynamical simulations for these coupled potential energy surfaces, utilizing the powerful multi-configuration time-dependent Hartree method are performed. Ultrafast internal conversion processes and the analysis of the MATI and photo-electron spectra shed new light

  6. On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

    Science.gov (United States)

    Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

    2014-10-28

    The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) water water in the hydration shell of anions.

  7. Construction of Vibronic Diabatic Hamiltonian for Excited-State Electron and Energy Transfer Processes.

    Science.gov (United States)

    Xie, Yu; Jiang, Shengshi; Zheng, Jie; Lan, Zhenggang

    2017-12-21

    Photoinduced excited-state electron and energy transfer processes are crucial in biological photoharvesting systems and organic photovoltaic devices. We discuss the construction of a diabatic vibronic Hamiltonian for the proper treatment of these processes involving the projection approach acting on both electronic wave functions and vibrational modes. In the electronic part, the wave function projection approach is used to construct the diabatic Hamiltonian in which both local excited states and charge-transfer states are included on the same footing. For the vibrational degrees of freedom, the vibronic couplings in the diabatic Hamiltonian are obtained in the basis of the pseudonormal modes localized on each monomer site by applying delocalized-to-localized mode projection. This systematic approach allows us to construct the vibronic diabatic Hamiltonian in molecular aggregates.

  8. Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C–H Bond Activation

    Science.gov (United States)

    Yi, Chae S.; Lee, Do W.

    2010-01-01

    Summary The cationic ruthenium-hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly effective catalyst for the intermolecular olefination reaction of arylketones with cycloalkenes. The preliminary mechanistic analysis revealed that electrophilic ruthenium-vinyl complex is the key species for mediating both vinyl C–H bond activation and the dehydrative olefination steps of the coupling reaction. PMID:20567607

  9. 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.

  10. Engineering an all-optical route to ultracold molecules in their vibronic ground state

    OpenAIRE

    Koch, Christiane P.; Moszynski, Robert

    2008-01-01

    We propose an improved photoassociation scheme to produce ultracold molecules in their vibronic ground state for the generic case where non-adiabatic effects facilitating transfer to deeply bound levels are absent. Formation of molecules is achieved by short laser pulses in a Raman-like pump-dump process where an additional near-infrared laser field couples the excited state to an auxiliary state. The coupling due to the additional field effectively changes the shape of the excited state pote...

  11. Theory of Excitonic Delocalization for Robust Vibronic Dynamics in LH2.

    Science.gov (United States)

    Caycedo-Soler, Felipe; Lim, James; Oviedo-Casado, Santiago; van Hulst, Niek F; Huelga, Susana F; Plenio, Martin B

    2018-06-11

    Nonlinear spectroscopy has revealed long-lasting oscillations in the optical response of a variety of photosynthetic complexes. Different theoretical models that involve the coherent coupling of electronic (excitonic) or electronic-vibrational (vibronic) degrees of freedom have been put forward to explain these observations. The ensuing debate concerning the relevance of either mechanism may have obscured their complementarity. To illustrate this balance, we quantify how the excitonic delocalization in the LH2 unit of Rhodopseudomonas acidophila purple bacterium leads to correlations of excitonic energy fluctuations, relevant coherent vibronic coupling, and importantly, a decrease in the excitonic dephasing rates. Combining these effects, we identify a feasible origin for the long-lasting oscillations observed in fluorescent traces from time-delayed two-pulse single-molecule experiments performed on this photosynthetic complex and use this approach to discuss the role of this complementarity in other photosynthetic systems.

  12. 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

  13. Intermolecular vibronic spectroscopy of small van der Waals clusters: Phenol- and aniline-(argon)2 complexes

    International Nuclear Information System (INIS)

    Schmidt, M.; Mons, M.; Le Calve, J.

    1990-01-01

    We report the clear observation and assignment of the symmetric stretching and bending van der Waals modes in two three-body C 2ν complexes, phenol- and aniline-(Ar) 2 , using resonant two-photon ionization. (orig.)

  14. VIBRONIC PROGRESSIONS IN SEVERAL DIFFUSE INTERSTELLAR BANDS

    International Nuclear Information System (INIS)

    Duley, W. W.; Kuzmin, Stanislav

    2010-01-01

    A number of vibronic progressions based on low-energy vibrational modes of a large molecule have been found in the diffuse interstellar band (DIB) spectrum of HD 183143. Four active vibrational modes have been identified with energies at 5.18 cm -1 , 21.41 cm -1 , 31.55 cm -1 , and 34.02 cm -1 . The mode at 34.02 cm -1 was previously recognized by Herbig. Four bands are associated with this molecule, with origins at 6862.61 A, 6843.64 A, 6203.14 A, and 5545.11 A (14589.1 cm -1 , 14608.08 cm -1 , 16116.41 cm -1 , and 18028.9 cm -1 , respectively). The progressions are harmonic and combination bands are observed involving all modes. The appearance of harmonic, rather than anharmonic, terms in these vibronic progressions is consistent with torsional motion of pendant rings, suggesting that the carrier is a 'floppy' molecule. Some constraints on the type and size of the molecule producing these bands are discussed.

  15. Vibronic Spectroscopy of the Phenylcyanomethyl Radical

    Science.gov (United States)

    Mehta, Deepali N.; Kidwell, Nathanael M.; Zwier, Timothy S.

    2011-06-01

    Resonance stabilized radicals (RSRs) are thought to be key intermediates in the formation of larger molecules in planetary atmospheres. Given the nitrogen-rich atmosphere of Titan, and the prevalence of nitriles there, it is likely that nitrile and isonitrile RSRs could be especially important in pathways leading to the formation of more complex nitrogen-containing compounds and the aerosols ("tholins") that are ultimately produced. In this talk, the results of a gas phase, jet-cooled vibronic spectroscopy study of the phenylcyanomethyl radical (C_6H_5.{C}HCN), the nitrogen-containing analog of the 1-phenylpropargyl radical, will be presented. A resonant two color photon ionization spectrum over the range 21,350-22,200 Cm-1 (450.0-468.0 nm) has been recorded, and the D_0-D_1 origin band has been tentatively identified at 21,400 Cm-1. Studies identifying the ionization threshold, and characterizing the vibronic structure will also be presented. An analogous study of the phenylisocyanomethyl radical, C_6H_5.{C}HNC, is currently being pursued for comparison with that of phenylcyanomethyl radical.

  16. Enhanced fullerene–Au(111 coupling in (2√3 × 2√3R30° superstructures with intermolecular interactions

    Directory of Open Access Journals (Sweden)

    Michael Paßens

    2015-06-01

    Full Text Available Disordered and uniform (2√3 × 2√3R30° superstructures of fullerenes on the Au(111 surface have been studied using scanning tunneling microscopy and spectroscopy. It is shown that the deposition and growth process of a fullerene monolayer on the Au(111 surface determine the resulting superstructure. The supply of thermal energy is of importance for the activation of a Au vacancy forming process and thus, one criterion for the selection of the respective superstructure. However, here it is depicted that a vacancy–adatom pair can be formed even at room temperature. This latter process results in C60 molecules that appear slightly more bright in scanning tunnelling microscopy images and are identified in disordered (2√3 x 2√3R30° superstructures based on a detailed structure analysis. In addition, these slightly more bright C60 molecules form uniform (2√3 x 2√3R30° superstructures, which exhibit intermolecular interactions, likely mediated by Au adatoms. Thus, vacancy–adatom pairs forming at room temperature directly affect the resulting C60 superstructure. Differential conductivity spectra reveal a lifting of the degeneracy of the LUMO and LUMO+1 orbitals in the uniform (2√3 x 2√3R30° superstructure and in addition, hybrid fullerene–Au(111 surface states suggest partly covalent interactions.

  17. Desensitization of metastable intermolecular composites

    Science.gov (United States)

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

    2011-04-26

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

  18. Vibronic Boson Sampling: Generalized Gaussian Boson Sampling for Molecular Vibronic Spectra at Finite Temperature.

    Science.gov (United States)

    Huh, Joonsuk; Yung, Man-Hong

    2017-08-07

    Molecular vibroic spectroscopy, where the transitions involve non-trivial Bosonic correlation due to the Duschinsky Rotation, is strongly believed to be in a similar complexity class as Boson Sampling. At finite temperature, the problem is represented as a Boson Sampling experiment with correlated Gaussian input states. This molecular problem with temperature effect is intimately related to the various versions of Boson Sampling sharing the similar computational complexity. Here we provide a full description to this relation in the context of Gaussian Boson Sampling. We find a hierarchical structure, which illustrates the relationship among various Boson Sampling schemes. Specifically, we show that every instance of Gaussian Boson Sampling with an initial correlation can be simulated by an instance of Gaussian Boson Sampling without initial correlation, with only a polynomial overhead. Since every Gaussian state is associated with a thermal state, our result implies that every sampling problem in molecular vibronic transitions, at any temperature, can be simulated by Gaussian Boson Sampling associated with a product of vacuum modes. We refer such a generalized Gaussian Boson Sampling motivated by the molecular sampling problem as Vibronic Boson Sampling.

  19. 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).

  20. Vibronic oscillator strengths in cubic systems. I.- The adsorption spectrum of Tm+3

    International Nuclear Information System (INIS)

    Acevedo, R.; Hurtado, O.F.; Meruane, T.

    2000-01-01

    A symmetry adapted vibronic crystal field-ligand polarisation scheme is utilised with reference to the elpasolite type system, to gain understanding about the role played by both the electronic and the vibrational factors in the absorption intensity mechanisms of various selected excitation in this crystal. The calculation is performed assuming: The coupling among the internal and the external vibrations is negligible and therefore a seven atom system may be employed (though, we recognise that the vibrational frequencies values depend en several factors; among others the nature of both the host and the temperature. Additionally, no attempt has been made to include corrections due to spectral line shapes and to the shapes of the potential energy hypersurfaces associated with the terminal electronic terminal states). We have included some sophistication as for both the electronic and the vibrational wavefunctions are concerned. Three different set of electronic wavefunctions are reported and the sensitivity of the estimated overall vibronic intensities on both electronic and vibrational factors is tested against the experimental data , with reference to the 10K absorption spectrum. At this stage, we have excluded , the effects of both concentration and pressure upon the observed vibronic intensities, though new experiments and model calculations are needed. In this article, we report calculations for the whole set of transitions associated with the (a) , (b) and (c) .Our model calculation is based upon a minimum set of parameters to be fitted from experiment, mainly because. our main target is to advance the knowledge on mechanistic factors and the most likely paths for both emission and absorption for these type systems

  1. Vibronic coupling in the excited-states of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    Miki, Takeshi [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany; Buckup, Tiago [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany; Krause, Marie S. [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany; Southall, June [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow; UK; Cogdell, Richard J. [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow; UK; Motzkus, Marcus [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany

    2016-01-01

    The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S2to the optically dark state S1.

  2. Mixed-valence molecular four-dot unit for quantum cellular automata: Vibronic self-trapping and cell-cell response.

    Science.gov (United States)

    Tsukerblat, Boris; Palii, Andrew; Clemente-Juan, Juan Modesto; Coronado, Eugenio

    2015-10-07

    Our interest in this article is prompted by the vibronic problem of charge polarized states in the four-dot molecular quantum cellular automata (mQCA), a paradigm for nanoelectronics, in which binary information is encoded in charge configuration of the mQCA cell. Here, we report the evaluation of the electronic levels and adiabatic potentials of mixed-valence (MV) tetra-ruthenium (2Ru(ii) + 2Ru(iii)) derivatives (assembled as two coupled Creutz-Taube complexes) for which molecular implementations of quantum cellular automata (QCA) was proposed. The cell based on this molecule includes two holes shared among four spinless sites and correspondingly we employ the model which takes into account the two relevant electron transfer processes (through the side and through the diagonal of the square) as well as the difference in Coulomb energies for different instant positions of localization of the hole pair. The combined Jahn-Teller (JT) and pseudo JT vibronic coupling is treated within the conventional Piepho-Krauzs-Schatz model adapted to a bi-electronic MV species with the square-planar topology. The adiabatic potentials are evaluated for the low lying Coulomb levels in which the antipodal sites are occupied, the case just actual for utilization in mQCA. The conditions for the vibronic self-trapping in spin-singlet and spin-triplet states are revealed in terms of the two actual transfer pathways parameters and the strength of the vibronic coupling. Spin related effects in degrees of the localization which are found for spin-singlet and spin-triplet states are discussed. The polarization of the cell is evaluated and we demonstrate how the partial delocalization caused by the joint action of the vibronic coupling and electron transfer processes influences polarization of a four-dot cell. The results obtained within the adiabatic approach are compared with those based on the numerical solution of the dynamic vibronic problem. Finally, the Coulomb interaction between

  3. Ab initio ro-vibronic spectroscopy of SiCCl (X{sup ~2}Π)

    Energy Technology Data Exchange (ETDEWEB)

    Brites, Vincent [Université d’Evry Val d’Essonne, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, LAMBE CNRS UMR 8587, Boulevard F. Mitterrand, 91025 Evry Cedex (France); Mitrushchenkov, Alexander O.; Léonard, Céline, E-mail: celine.leonard@u-pem.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Peterson, Kirk A. [Department of Chemistry, Washington State University, Pullman, Washington 99164 (United States)

    2014-07-21

    The full dimensional potential energy surfaces of the {sup 2}A{sup ′} and {sup 2}A{sup ′′} electronic components of X{sup ~2}Π SiCCl have been computed using the explicitly correlated coupled cluster method, UCCSD(T)-F12b, combined with a composite approach taking into account basis set incompleteness, core-valence correlation, scalar relativity, and higher order excitations. The spin-orbit and dipole moment surfaces have also been computed ab initio. The ro-vibronic energy levels and absorption spectrum at 5 K have been determined from variational calculations. The influence of each correction on the fundamental frequencies is discussed. An assignment is proposed for bands observed in the LIF experiment of Smith et al. [J. Chem. Phys. 117, 6446 (2002)]. The overall agreement between the experimental and calculated ro-vibronic levels is better than 7 cm{sup −1} which is comparable with the 10–20 cm{sup −1} resolution of the emission spectrum.

  4. The characterization of the high-frequency vibronic contributions to the 77 K emission spectra of ruthenium-am(m)ine-bipyridyl complexes, their attenuation with decreasing energy gaps, and the implications of strong electronic coupling for inverted-region electron transfer.

    Science.gov (United States)

    Xie, Puhui; Chen, Yuan-Jang; Uddin, Md Jamal; Endicott, John F

    2005-06-02

    The 77 K emission spectra of a series of [Ru(Am)6-2n(bpy)n]2+ complexes (n = 1-3) have been determined in order to evaluate the effects of appreciable excited state (e)/ground state (g) configurational mixing on the properties of simple electron-transfer systems. The principal focus is on the vibronic contributions, and the correlated distortions of the bipyridine ligand in the emitting MLCT excited state. To address the issues that are involved, the emission band shape at 77 K is interpreted as the sum of a fundamental component, corresponding to the {e,0'} --> {g,0} transition, and progressions in the ground-state vibrational modes that correlate with the excited-state distortion. Literature values of the vibrational parameters determined from the resonance-Raman (rR) for [Ru(NH3)4bpy]2+ and [Ru(bpy)3]2+ are used to model the emission spectra and to evaluate the spectral analysis. The Gaussian fundamental component with an energy Ef and bandwidth Deltanu1/2 is deconvoluted from the observed emission spectrum. The first-, second-, and third-order terms in the progressions of the vibrational modes that contribute to the band shape are evaluated as the sums of Gaussian-shaped contributions of width Deltanu1/2. The fundamental and the rR parameters give an excellent fit of the observed emission spectrum of [Ru(NH3)4bpy]2+, but not as good for the [Ru(bpy)3]2+ emission spectrum probably because the Franck-Condon excited state probed by the rR is different in symmetry from the emitting MLCT excited state. Variations in vibronic contributions for the series of complexes are evaluated in terms of reorganizational energy profiles (emreps, Lambdax) derived from the observed spectra, and modeled using the rR parameters. This modeling demonstrates that most of the intensity of the vibronic envelopes obtained from the frozen solution emission spectra arises from the overlapping of first-order vibronic contributions of significant bandwidth with additional convoluted

  5. Vibrational and vibronic coherences in the dynamics of the FMO complex

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaomeng; Kühn, Oliver, E-mail: oliver.kuehn@uni-rostock.de

    2016-12-20

    The coupled exciton–vibrational dynamics of a seven site Frenkel exciton model of the Fenna–Matthews–Olson (FMO) complex is investigated using a Quantum Master Equation approach. Thereby, one vibrational mode per monomer is treated explicitly as being part of the relevant system. Emphasis is put on the comparison of this model with that of a purely excitonic relevant system. Further, the effects of two different approximations to the exciton–vibrational basis are investigated, namely the one- and two-particle description. Analysis of the vibronic and vibrational density matrix in the site basis points to the importance of on- and inter-site coherences for the exciton transfer. Here, one- and two-particle approximations give rise to qualitatively different results.

  6. 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.)

  7. Non vertical vibronic transitions in atom molecule collisions

    International Nuclear Information System (INIS)

    Klomp, U.C.

    1982-01-01

    This thesis is mainly devoted to an experimental and theoretical study on vibronic transitions which occur in collisions between an alkali atom and several diatomic molecules. An experimental study on electron and ion production in repulsive Cs-CO and Cs-N 2 collisions, and in Cs-NO and Cs-O 2 non-repulsive collisions is presented. The experimental data are discussed in terms of some existing models. It is clear that a new consistent theory on vibronic transitions is needed to explain the experimental data. Such a theory is presented, and it is shown that some existing models are limiting cases of this theory. An experimental study on the relative probabilities for ion and electron production in collisions between a Na, K or Cs atom and an O 2 or NO molecule is also described. These experiments suggest that the incident velocity of the alkali atoms has a predominant influence on the relative probabilities for ion and electron production in these collisions. (Auth.)

  8. Quasi-classical approaches to vibronic spectra revisited

    Science.gov (United States)

    Karsten, Sven; Ivanov, Sergei D.; Bokarev, Sergey I.; Kühn, Oliver

    2018-03-01

    The framework to approach quasi-classical dynamics in the electronic ground state is well established and is based on the Kubo-transformed time correlation function (TCF), being the most classical-like quantum TCF. Here we discuss whether the choice of the Kubo-transformed TCF as a starting point for simulating vibronic spectra is as unambiguous as it is for vibrational ones. Employing imaginary-time path integral techniques in combination with the interaction representation allowed us to formulate a method for simulating vibronic spectra in the adiabatic regime that takes nuclear quantum effects and dynamics on multiple potential energy surfaces into account. Further, a generalized quantum TCF is proposed that contains many well-established TCFs, including the Kubo one, as particular cases. Importantly, it also provides a framework to construct new quantum TCFs. Applying the developed methodology to the generalized TCF leads to a plethora of simulation protocols, which are based on the well-known TCFs as well as on new ones. Their performance is investigated on 1D anharmonic model systems at finite temperatures. It is shown that the protocols based on the new TCFs may lead to superior results with respect to those based on the common ones. The strategies to find the optimal approach are discussed.

  9. Mixed-Valence Molecular Unit for Quantum Cellular Automata: Beyond the Born-Oppenheimer Paradigm through the Symmetry-Assisted Vibronic Approach.

    Science.gov (United States)

    Clemente-Juan, Juan Modesto; Palii, Andrew; Coronado, Eugenio; Tsukerblat, Boris

    2016-08-09

    In this article, we focus on the electron-vibrational problem of the tetrameric mixed-valence (MV) complexes proposed for implementation as four-dot molecular quantum cellular automata (mQCA).1 Although the adiabatic approximation explored in ref 2 is an appropriate tool for the qualitative analysis of the basic characteristics of mQCA, like vibronic trapping of the electrons encoding binary information and cell-cell response, it loses its accuracy providing moderate vibronic coupling and fails in the description of the discrete pattern of the vibronic levels. Therefore, a precise solution of the quantum-mechanical vibronic problem is of primary importance for the evaluation of the shapes of the electron transfer optical absorption bands and quantitative analysis of the main parameters of tetrameric quantum cells. Here, we go beyond the Born-Oppenheimer paradigm and present a solution of the quantum-mechanical pseudo Jahn-Teller (JT) vibronic problem in bielectronic MV species (exemplified by the tetra-ruthenium complexes) based on the recently developed symmetry-assisted approach.3,4 The mathematical approach to the vibronic eigenproblem takes into consideration the point symmetry basis, and therefore, the total matrix of the JT Hamiltonian is blocked to the maximum extent. The submatrices correspond to the irreducible representations (irreps) of the point group. With this tool, we also extend the theory of the mQCA cell beyond the limit of prevailing Coulomb repulsion in the electronic pair (adopted in ref 2), and therefore, the general pseudo-JT problems for spin-singlet ((1)B1g, 2(1)A1g, (1)B2g, (1)Eu) ⊗ (b1g + eu) and spin-triplet states ((3)A2g, (3)B1g, 2(3)Eu) ⊗ (b1g + eu) in a square-planar bielectronic system are solved. The obtained symmetry-adapted electron-vibrational functions are employed for the calculation of the profiles (shape functions) of the charge transfer absorption bands in the tetrameric MV complexes and for the discussion of the

  10. Desensitization and recovery of metastable intermolecular composites

    Science.gov (United States)

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

    2010-09-07

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

  11. 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.

  12. Structural changes and intermolecular interactions of filled ice Ic structure for hydrogen hydrate under high pressure

    International Nuclear Information System (INIS)

    Machida, S; Hirai, H; Kawamura, T; Yamamoto, Y; Yagi, T

    2010-01-01

    High-pressure experiments of hydrogen hydrate were performed using a diamond anvil cell under conditions of 0.1-44.2 GPa and at room temperature. Also, high pressure Raman studies of solid hydrogen were performed in the pressure range of 0.1-43.7 GPa. X-ray diffractometry (XRD) for hydrogen hydrate revealed that a known high-pressure structure, filled ice Ic structure, of hydrogen hydrate transformed to a new high-pressure structure at approximately 35-40 GPa. A comparison of the Raman spectroscopy of a vibron for hydrogen molecules between hydrogen hydrate and solid hydrogen revealed that the extraction of hydrogen molecules from hydrogen hydrate occurred above 20 GPa. Also, the Raman spectra of a roton revealed that the rotation of hydrogen molecules in hydrogen hydrate was suppressed at around 20 GPa and that the rotation recovered under higher pressure. These results indicated that remarkable intermolecular interactions in hydrogen hydrate between neighboring hydrogen molecules and between guest hydrogen molecules and host water molecules might occur. These intermolecular interactions could produce the stability of hydrogen hydrate.

  13. Vibronic spectra of Gd3+ in metaphosphate glasses: Comparison with Raman and infrared spectra

    International Nuclear Information System (INIS)

    Hall, D.W.; Brawer, S.A.; Weber, M.J.

    1982-01-01

    Vibronic sidebands associated with the 6 P/sub 7/2/→ 8 S/sub 7/2/ transition of Gd 3+ -doped metaphosphate glasses are observed using line-narrowed fluorescence techniques. Glasses having metal cations of different mass and charge (La,Al,Mg,Ba) are examined. Vibronic spectra, which probe vibrations about the rare-earth element site, are compared with polarized Raman scattering data and the infrared dielectric constant obtained from near-normal reflectance measurements. Results indicate that in metaphosphate glasses vibronic selection rules are similar to HV (vertical height) Raman selection rules. The wavelengths and relative intensities of peaks in the high-frequency portion of the vibronic spectra change with respect to corresponding peaks in the Raman spectra when the mass and/or charge of Gd 3+ differs significantly from that of the metal cation

  14. Characterizing the Polymer:Fullerene Intermolecular Interactions

    KAUST Repository

    Sweetnam, Sean; Vandewal, Koen; Cho, Eunkyung; Risko, Chad; Coropceanu, Veaceslav; Salleo, Alberto; Bredas, Jean-Luc; McGehee, Michael D.

    2016-01-01

    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

  15. Toward a general mixed quantum/classical method for the calculation of the vibronic ECD of a flexible dye molecule with different stable conformers: Revisiting the case of 2,2,2-trifluoro-anthrylethanol.

    Science.gov (United States)

    Cerezo, Javier; Aranda, Daniel; Avila Ferrer, Francisco J; Prampolini, Giacomo; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Santoro, Fabrizio

    2018-06-01

    We extend a recently proposed mixed quantum/classical method for computing the vibronic electronic circular dichroism (ECD) spectrum of molecules with different conformers, to cases where more than one hindered rotation is present. The method generalizes the standard procedure, based on the simple Boltzmann average of the vibronic spectra of the stable conformers, and includes the contribution of structures that sample all the accessible conformational space. It is applied to the simulation of the ECD spectrum of (S)-2,2,2-trifluoroanthrylethanol, a molecule with easily interconvertible conformers, whose spectrum exhibits a pattern of alternating positive and negative vibronic peaks. Results are in very good agreement with experiment and show that spectra averaged over all the sampled conformational space can deviate significantly from the simple average of the contributions of the stable conformers. The present mixed quantum/classical method is able to capture the effect of the nonlinear dependence of the rotatory strength on the molecular structure and of the anharmonic couplings among the modes responsible for molecular flexibility. Despite its computational cost, the procedure is still affordable and promises to be useful in all cases where the ECD shape arises from a subtle balance between vibronic effects and conformational variety. © 2018 Wiley Periodicals, Inc.

  16. Ab initio study of vibronic transitions between x2π and 12Σ+ electronic states of HCP+ ion

    Directory of Open Access Journals (Sweden)

    Stojanović Ljiljana

    2013-01-01

    Full Text Available The ground and low-lying excited doublet electronic states of the HCP+ ion were studied by means of multireference configuration interaction method. Vibronic energy levels of the X2Π state of Σ, Π, Δ, and Φ symmetry, up to the 2500 cm-1, have been calculated variationally, employing previously developed ab initio methods which take into account vibronic and spin-orbit interactions. Obtained vibronic wave functions were used to estimate transition moments between vibronic energy levels of the X2Π and 12Σ+ electronic states. Results were compared to available experimental and theoretical data. [Projekat Ministarstva nauke Republike Srbije, br. 172040

  17. E x circle epsilon Jahn-Teller anharmonic coupling for an octahedral system

    CERN Document Server

    Avram, N M; Kibler, M R

    2001-01-01

    The coupling between doubly degenerate electronic states and doubly degenerate vibrations is analyzed for an octahedral system on the basis of the introduction of an anharmonic Morse potential for the vibronic part. The vibrations are described by anharmonic coherent states and their linear coupling with the electronic states is considered. The matrix elements of the vibronic interaction are built and the energy levels corresponding to the interaction Hamiltonian are derived.

  18. Understanding the electron-phonon interaction in polar crystals: Perspective presented by the vibronic theory

    Science.gov (United States)

    Pishtshev, A.; Kristoffel, N.

    2017-05-01

    We outline our novel results relating to the physics of the electron-TO-phonon (el-TO-ph) interaction in a polar crystal. We explained why the el-TO-ph interaction becomes effectively strong in a ferroelectric, and showed how the electron density redistribution establishes favorable conditions for soft-behavior of the long-wavelength branch of the active TO vibration. In the context of the vibronic theory it has been demonstrated that at the macroscopic level the interaction of electrons with the polar zone-centre TO phonons can be associated with the internal long-range dipole forces. Also we elucidated a methodological issue of how local field effects are incorporated within the vibronic theory. These result provided not only substantial support for the vibronic mechanism of ferroelectricity but also presented direct evidence of equivalence between vibronic and the other lattice dynamics models. The corresponding comparison allowed us to introduce the original parametrization for constants of the vibronic interaction in terms of key material constants. The applicability of the suggested formula has been tested for a wide class of polar materials.

  19. Observation of vibronic emission spectrum of jet-cooled 3,5-difluorobenzyl radical.

    Science.gov (United States)

    Lee, Seung Woon; Yoon, Young Wook; Lee, Sang Kuk

    2010-09-02

    We applied the technique of corona-excited supersonic expansion using a pinhole-type glass nozzle to observe the vibronic emission spectrum of jet-cooled benzyl-type radicals from the corona discharge of precursor 3,5-difluorotoluene seeded in a large amount of inert helium carrier gas. The vibronically well-resolved emission spectrum was recorded with a long-path monochromator in the visible region. After subtracting the vibronic bands originating from isomeric difluorobenzyl radicals from the observed spectrum, we identified for the first time the bands belonging to the 3,5-difluorobenzyl radical, from which the electronic energy and vibrational mode frequencies of the 3,5-difluorobenzyl radical were accurately determined in the ground electronic state by comparison with those of the precursor and with those from an ab initio calculation.

  20. Vibron Solitons and Soliton-Induced Infrared Spectra of Crystalline Acetanilide

    Science.gov (United States)

    Takeno, S.

    1986-01-01

    Red-shifted infrared spectra at low temperatures of amide I (C=O stretching) vibrations of crystalline acetanilide measured by Careri et al. are shown to be due to vibron solitons, which are nonlinearity-induced localized modes of vibrons arising from their nonlinear interactions with optic-type phonons. A nonlinear eigenvalue equation giving the eigenfrequency of stationary solitons is solved approximately by introducing lattice Green's functions, and the obtained result is in good agreement with the experimental result. Inclusion of interactions with acoustic phonons yields the Debye-Waller factor in the zero-phonon line spectrum of vibron solitons, in a manner analogous to the case of impurity-induced localized harmonic phonon modes in alkali halides.

  1. 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...

  2. Two-vibron bound states in the β–Fermi–Pasta–Ulam model

    International Nuclear Information System (INIS)

    Hu Xinguang; Tang Yi

    2008-01-01

    This paper studies the two-vibron bound states in the β–Fermi–Pasta–Ulam model by means of the number conserving approximation combined with the number state method. The results indicate that on-site, adjacent-site and mixed two-vibron bound states may exist in the model. Specially, wave number has a significant effect on such bound states, which may be considered as the quantum effects of the localized states in quantum systems. (condensed matter: structure, thermal and mechanical properties)

  3. Effect of molecular weight on the vibronic structure of a diketopyrrolopyrrole polymer

    KAUST Repository

    Hayes, Sophia C.

    2016-09-27

    Resonance Raman Spectroscopy (RRS) is employed in this study to examine the influence of molecular weight on the optical response of a diketopyrrolopyrrole polymer (DPP-TT-T) in solution. The vibronic structure observed for the ground state absorption of this polymer is found to vary with molecular weight and solvent. Resonance Raman Intensity Analysis (RRIA) revealed that the absorption spectra can be described by at least two dipole-allowed transitions and the vibronic structure variation is due to differing contributions from linear and curved segments of the polymer.

  4. Effect of molecular weight on the vibronic structure of a diketopyrrolopyrrole polymer

    KAUST Repository

    Hayes, Sophia C.; Pieridou, Galatia; Vezie, Michelle; Few, Sheridan; Bronstein, Hugo; Meager, Iain; McCulloch, Iain; Nelson, Jenny

    2016-01-01

    Resonance Raman Spectroscopy (RRS) is employed in this study to examine the influence of molecular weight on the optical response of a diketopyrrolopyrrole polymer (DPP-TT-T) in solution. The vibronic structure observed for the ground state absorption of this polymer is found to vary with molecular weight and solvent. Resonance Raman Intensity Analysis (RRIA) revealed that the absorption spectra can be described by at least two dipole-allowed transitions and the vibronic structure variation is due to differing contributions from linear and curved segments of the polymer.

  5. Intermolecular interaction potentials of the methane dimer from the local density approximation

    International Nuclear Information System (INIS)

    Chen Xiangrong; Bai Yulin; Zhu Jun; Yang Xiangdong

    2004-01-01

    The intermolecular interaction potentials of methane (CH 4 ) dimer are calculated within the density functional theory in the local density approximation (LDA). It is found that the calculated potentials have minima when the intermolecular distance of CH 4 dimer is about 7.0 a.u., which is in good agreement with the experiment. The depth of the potential is 0.017 eV. The results obtained by our LDA calculations seem to agree well with those obtained by MP2, MP3, and CCSD from the Moeller-Plesset and coupled cluster methods by Tsuzuki et al. and with the experimental data

  6. Tunneling Splittings in Vibronic Structure of CH_3F^+ ( X^2E): Studied by High Resolution Photoelectron Spectra and AB Initio Theoretical Method

    Science.gov (United States)

    Mo, Yuxiang; Gao, Shuming; Dai, Zuyang; Li, Hua

    2013-06-01

    We report a combined experimental and theoretical study on the vibronic structure of CH_3F^+. The results show that the tunneling splittings of vibrational energy levels occur in CH_3F^+ due to the Jahn-Teller effect. Experimentally, we have measured a high resolution ZEKE spectrum of CH_3F up to 3500 cm^-^1 above the ground state. Theoretically, we performed an ab initio calculation based on the diabatic model. The adiabatic potential energy surfaces (APES) of CH_3F^+ have been calculated at the MRCI/CAS/avq(t)z level and expressed by Taylor expansions with normal coordinates as variables. The energy gradients for the lower and upper APES, the derivative couplings between them and also the energies of the APES have been used to determine the coefficients in the Taylor expansion. The spin-vibronic energy levels have been calculated by accounting all six vibrational modes and their couplings. The experimental ZEKE spectra were assigned based on the theoretical calculations. W. Domcke, D. R. Yarkony, and H. Köpple (Eds.), Conical Intersections: Eletronic Structure, Dynamics and Spectroscopy (World Scientific, Singapore, 2004). M. S. Schuurman, D. E. Weinberg, and D. R. Yarkony, J. Chem. Phys. 127, 104309 (2007).

  7. Vibronic-structure tracking: A shortcut for vibrationally resolved UV/Vis-spectra calculations

    Energy Technology Data Exchange (ETDEWEB)

    Barton, Dennis; König, Carolin; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de [Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster (Germany)

    2014-10-28

    The vibrational coarse structure and the band shapes of electronic absorption spectra are often dominated by just a few molecular vibrations. By contrast, the simulation of the vibronic structure even in the simplest theoretical models usually requires the calculation of the entire set of normal modes of vibration. Here, we exploit the idea of the mode-tracking protocol [M. Reiher and J. Neugebauer, J. Chem. Phys. 118, 1634 (2003)] in order to directly target and selectively calculate those normal modes which have the largest effect on the vibronic band shape for a certain electronic excitation. This is achieved by defining a criterion for the importance of a normal mode to the vibrational progressions in the absorption band within the so-called “independent mode, displaced harmonic oscillator” (IMDHO) model. We use this approach for a vibronic-structure investigation for several small test molecules as well as for a comparison of the vibronic absorption spectra of a truncated chlorophyll a model and the full chlorophyll a molecule. We show that the method allows to go beyond the often-used strategy to simulate absorption spectra based on broadened vertical excitation peaks with just a minimum of computational effort, which in case of chlorophyll a corresponds to about 10% of the cost for a full simulation within the IMDHO approach.

  8. Vibronic relaxation in molecular mixed crystals : Pentacene in naphthalene and p-terphenyl

    NARCIS (Netherlands)

    Hesselink, Wim H.; Wiersma, Douwe A.

    1981-01-01

    Picosecond photon echo techniques are used to measure directly vibronic relaxation times in the first excited singlet state of pentacene in naphthalene and p-terphenyl. In regions of low (< 300 cm–1) and high (> 1000 cm–1) vibrational energy, relaxation is fast (τ <2 ps) due to direct phonon

  9. Digital communication through intermolecular fluorescence modulation.

    Science.gov (United States)

    Raymo, F M; Giordani, S

    2001-06-14

    [see reaction]. Ultraminiaturized processors incorporating molecular components can be developed only after devising efficient strategies to communicate signals at the molecular level. We have demonstrated that a three-state molecular switch responds to ultraviolet light, visible light, and H+, attenuating the emission intensity of a fluorescent probe. Intermolecular communication is responsible for the transduction of three input signals into a single optical output. The behavior of the communicating ensemble of molecules corresponds to that of a logic circuit incorporating seven gates.

  10. Vibronic Rabi resonances in harmonic and hard-wall ion traps for arbitrary laser intensity and detuning

    International Nuclear Information System (INIS)

    Lizuain, I.; Muga, J. G.

    2007-01-01

    We investigate laser-driven vibronic transitions of a single two-level atomic ion in harmonic and hard-wall traps. In the Lamb-Dicke regime, for tuned or detuned lasers with respect to the internal frequency of the ion, and weak or strong laser intensities, the vibronic transitions occur at well-isolated Rabi resonances, where the detuning-adapted Rabi frequency coincides with the transition frequency between vibrational modes. These vibronic resonances are characterized as avoided crossings of the dressed levels (eigenvalues of the full Hamiltonian). Their peculiarities due to symmetry constraints and trapping potential are also examined

  11. Intermolecular interactions in the condensed phase

    DEFF Research Database (Denmark)

    Christensen, Anders S.; Kromann, Jimmy Charnley; Jensen, Jan Halborg

    2017-01-01

    To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy...... and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need...

  12. Phase sensitive control of vibronic guest-host interaction: Br2 in Ar matrix.

    Science.gov (United States)

    Ibrahim, Heide; Héjjas, Mónika; Fushitani, Mizuho; Schwentner, Nikolaus

    2009-07-02

    Vibronic progressions are programmed into a pulse shaper which converts them via the inherent Fourier transformation into a train of femtosecond pulses in time domain for chromophore excitation. Double pulse results agree with phase-sensitive wave packet superposition from a Michelson interferometer which delivers coherence times with high reliability. Spectral resolution of 1 nm and a spacing of around 4 nm within the 20 nm envelope centered at 590 nm delivers a train of seven phase-controlled 40 fs subpulses separated by 250 fs. Combs adjusted to the zero phonon lines (ZPL) and phonon sidebands (PSB) of the B state vibronic progression are reproduced in the chromophore for a coherent subpulse accumulation. B state ZPL wave packet dynamics dominates in pump-probe spectra due to its coherence despite an overwhelming but incoherent A state contribution in absorption. PSB comb accumulation is also phase sensitive and demonstrates coherence within several 100 matrix degrees of freedom in the vicinity.

  13. Selective two-photon excitation of a vibronic state by correlated photons.

    Science.gov (United States)

    Oka, Hisaki

    2011-03-28

    We theoretically investigate the two-photon excitation of a molecular vibronic state by correlated photons with energy anticorrelation. A Morse oscillator having three sets of vibronic states is used, as an example, to evaluate the selectivity and efficiency of two-photon excitation. We show that a vibrational mode can be selectively excited with high efficiency by the correlated photons, without phase manipulation or pulse-shaping techniques. This can be achieved by controlling the quantum correlation so that the photon pair concurrently has two pulse widths, namely, a temporally narrow width and a spectrally narrow width. Though this concurrence is seemingly contradictory, we can create such a photon pair by tailoring the quantum correlation between two photons.

  14. Organic Microcrystal Vibronic Lasers with Full-Spectrum Tunable Output beyond the Franck-Condon Principle.

    Science.gov (United States)

    Dong, Haiyun; Zhang, Chunhuan; Liu, Yuan; Yan, Yongli; Hu, Fengqin; Zhao, Yong Sheng

    2018-03-12

    The very broad emission bands of organic semiconductor materials are, in theory, suitable for achieving versatile solid-state lasers; however, most of organic materials only lase at short wavelength corresponding to the 0-1 transition governed by the Franck-Condon (FC) principle. A strategy is developed to overcome the limit of FC principle for tailoring the output of microlasers over a wide range based on the controlled vibronic emission of organic materials at microcrystal state. For the first time, the output wavelength of organic lasers is tailored across all vibronic (0-1, 0-2, 0-3, and even 0-4) bands spanning the entire emission spectrum. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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

  16. Rotational Parameters from Vibronic Eigenfunctions of Jahn-Teller Active Molecules

    Science.gov (United States)

    Garner, Scott M.; Miller, Terry A.

    2017-06-01

    The structure in rotational spectra of many free radical molecules is complicated by Jahn-Teller distortions. Understanding the magnitudes of these distortions is vital to determining the equilibrium geometric structure and details of potential energy surfaces predicted from electronic structure calculations. For example, in the recently studied {\\widetilde{A}^2E^{''} } state of the NO_3 radical, the magnitudes of distortions are yet to be well understood as results from experimental spectroscopic studies of its vibrational and rotational structure disagree with results from electronic structure calculations of the potential energy surface. By fitting either vibrationally resolved spectra or vibronic levels determined by a calculated potential energy surface, we obtain vibronic eigenfunctions for the system as linear combinations of basis functions from products of harmonic oscillators and the degenerate components of the electronic state. Using these vibronic eigenfunctions we are able to predict parameters in the rotational Hamiltonian such as the Watson Jahn-Teller distortion term, h_1, and compare with the results from the analysis of rotational experiments.

  17. Energy spectra of vibron and cluster models in molecular and nuclear systems

    Science.gov (United States)

    Jalili Majarshin, A.; Sabri, H.; Jafarizadeh, M. A.

    2018-03-01

    The relation of the algebraic cluster model, i.e., of the vibron model and its extension, to the collective structure, is discussed. In the first section of the paper, we study the energy spectra of vibron model, for diatomic molecule then we derive the rotation-vibration spectrum of 2α, 3α and 4α configuration in the low-lying spectrum of 8Be, 12C and 16O nuclei. All vibrational and rotational states with ground and excited A, E and F states appear to have been observed, moreover the transitional descriptions of the vibron model and α-cluster model were considered by using an infinite-dimensional algebraic method based on the affine \\widehat{SU(1,1)} Lie algebra. The calculated energy spectra are compared with experimental data. Applications to the rotation-vibration spectrum for the diatomic molecule and many-body nuclear clusters indicate that there are solvable models and they can be approximated very well using the transitional theory.

  18. Vibronic intensities for Er3+ in Cs2 NaErCl6

    International Nuclear Information System (INIS)

    Acevedo, R.; Navarro, G.; Meruane, T.

    2001-01-01

    In this current study, we have undertaken vibronic intensity calculations for the absorptions (( 4 I 15/2 ) Γ k ) → (( 4 I 13/2 ) Γ l ) of the Er 3+ in the Cs 2 NaErCl 6 elpasolite type system. This system is extremely complicated to handle from both a theoretical and an experimental viewpoints. This theoretical work shows that over an energy range of about 400 cm -1 , a substantial amount of transitions are likely to take place (about 100 transitions; twenty five of them are magnetic dipole allowed and seventy five are vibronically allowed). It is then a formidable task to identify and assign all of these transitions in a non-ambiguous way. Also the experimental evidence available for these absorptions is related to a total of about twenty lines in the luminescence spectrum of this system. The spectrum itself is very challenging and the superposition of spectral features is most likely to occur. A careful analysis of the calculated vibronic intensities and overall oscillator strengths for the various transitions indicates that the current model used is both flexible and appropriate to deal with this kind of systems. In a forthcoming paper, we will examine the rather unusual high intensity associated with the (( 4 I 15/2 ) Γ k ) → (( 4 S 3/2 ) Γ l ) excitations. (Author)

  19. Couplings

    Science.gov (United States)

    Stošić, Dušan; Auroux, Aline

    Basic principles of calorimetry coupled with other techniques are introduced. These methods are used in heterogeneous catalysis for characterization of acidic, basic and red-ox properties of solid catalysts. Estimation of these features is achieved by monitoring the interaction of various probe molecules with the surface of such materials. Overview of gas phase, as well as liquid phase techniques is given. Special attention is devoted to coupled calorimetry-volumetry method. Furthermore, the influence of different experimental parameters on the results of these techniques is discussed, since it is known that they can significantly influence the evaluation of catalytic properties of investigated materials.

  20. Coupled quantum treatment of vibrationally inelastic and vibronic charge transfer in proton-O2 collisions

    International Nuclear Information System (INIS)

    Gianturco, F.A.; Palma, A.; Semprini, E.; Stefani, F.; Baer, M.

    1990-01-01

    A three-dimensional quantum-mechanical study of vibrational, state-resolved differential cross sections (DCS) for the direct inelastic and for the charge-transfer scattering channels has been carried out for the H + +O 2 system. The collision energy considered was E c.m. =23.0 eV, which is the same as that examined by Noll and Toennies in their experiments [J. Chem. Phys. 85, 3313 (1986)]. The scattering treatment employed was the charge-transfer infinite-order sudden approximation (CT IOSA) with the vibrational states correctly expanded over the relevant adiabatic basis for each of the two electronic channels. The state-to-state DCS are found to follow closely the behavior of the experimental quantities, both in the inelastic and the charge-transfer channels. Moreover, a careful comparison between the measured relative probabilities and computed values allows us to test in minute detail the efficiency of the scattering model and the reliability of the potential-energy surfaces employed. It is found that vibrational energy transfer is overestimated in the vibrational inelastic channels while in the charge-transfer inelastic channels the same energy transfer is slightly underestimated by the calculations. The total flux distribution, however, is found to be in very good accord with experiments. Angular distributions are also well reproduced both by the DCS and by the average energy-transfer values. The study of some of the CT IOSA quantities also allows us to establish clearly the importance of nonadiabatic transitions in enhancing vibrational inelasticity in the present system

  1. 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.

  2. Meson and baryon families as vibronic states in sl(2) quantum universal enveloping algebra

    International Nuclear Information System (INIS)

    Iwao, Syurei; Ono, Yasuji

    1990-01-01

    A mass formula of the q-deformed modified harmonic oscillator type in the sl(2) quantum universal enveloping algebra is proposed for the meson and baryon families, by taking into account the known theories as a guide. Specifying the vibronic quantum number, the deformation parameter and associated ones of the theory are determined from available data for the scalar, pseudoscalar, vector meson and baryon families. The parameters determined from totally ten families not only predict many unobserved states, but also give restrictions on the observable number of states. The method may admit taking into account non-perturbative effects. (author)

  3. Mechanism of Intermolecular Electron Transfer in Bionanostructures

    Science.gov (United States)

    Gruodis, A.; Galikova, N.; Šarka, K.; Saulė, R.; Batiuškaitė, D.; Saulis, G.

    Hepatocellular carcinoma (HCC) is one of the most common malignant tumors worldwide. Most patients are inoperable and hepatoma cells are resistant to conventional chemotherapies. Thus, the development of novel therapies for HCC treatment is of paramount importance. Amongst different alimentary factors, vitamin C and vitamin K3 In the present work, it has been shown that the treatment of mouse hepatoma MH-22A cells by vitamin C and vitamin K3 at the ratio of 100:1 greatly enhanced their cytotoxicity. When cells were subjected to vitamin C at 200 μM or to vitamin K3 at 2 μM separately, their viability reduced by only about 10%. However, when vitamins C and K3 were combined at the same concentrations, they killed more than 90% of cells. To elucidate the mechanism of the synergistic cytotoxicity of the C&K3 mixture, theoretical quantum-chemical analysis of the dynamics of intermolecular electron transfer (IET) processes within the complexes containing C (five forms) and K3 (one form) has been carried out. Optimization of the ground state complex geometry has been provided by means of GAUSSIAN03 package. Simulation of the IET has been carried out using NUVOLA package, in the framework of molecular orbitals (MO). The rate of IET has been calculated using Fermi Golden rule. The results of simulations allow us to create the preliminary model of the reaction pathway.

  4. 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.

  5. Measuring Intermolecular Binding Energies by Laser Spectroscopy.

    Science.gov (United States)

    Knochenmuss, Richard; Maity, Surajit; Féraud, Géraldine; Leutwyler, Samuel

    2017-02-22

    The ground-state dissociation energy, D0(S0), of isolated intermolecular complexes in the gas phase is a fundamental measure of the interaction strength between the molecules. We have developed a three-laser, triply resonant pump-dump-probe technique to measure dissociation energies of jet-cooled M•S complexes, where M is an aromatic chromophore and S is a closed-shell 'solvent' molecule. Stimulated emission pumping (SEP) via the S0→S1 electronic transition is used to precisely 'warm' the complex by populating high vibrational levels v" of the S0 state. If the deposited energy E(v") is less than D0(S0), the complex remains intact, and is then mass- and isomer-selectively detected by resonant two-photon ionization (R2PI) with a third (probe) laser. If the pumped level is above D0(S0), the hot complex dissociates and the probe signal disappears. Combining the fluorescence or SEP spectrum of the cold complex with the SEP breakoff of the hot complex brackets D0(S0). The UV chromophores 1-naphthol and carbazole were employed; these bind either dispersively via the aromatic rings, or form a hydrogen bond via the -OH or -NH group. Dissociation energies have been measured for dispersively bound complexes with noble gases (Ne, Kr, Ar, Xe), diatomics (N2, CO), alkanes (methane to n-butane), cycloalkanes (cyclopropane to cycloheptane), and unsaturated compounds (ethene, benzene). Hydrogen-bond dissociation energies have been measured for H2O, D2O, methanol, ethanol, ethers (oxirane, oxetane), NH3 and ND3.

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

    African Journals Online (AJOL)

    ADOWIE PERE

    Intermolecular Model Potentials and Virial Coefficients from Acoustic Data. 1* ... method of cluster expansion. Its merit is that, ... their determination is by the analyses of isothermal p- ρ-y data ... Carlo simulation method to calculate volumetric.

  7. Simulating quantum search algorithm using vibronic states of I2 manipulated by optimally designed gate pulses

    International Nuclear Information System (INIS)

    Ohtsuki, Yukiyoshi

    2010-01-01

    In this paper, molecular quantum computation is numerically studied with the quantum search algorithm (Grover's algorithm) by means of optimal control simulation. Qubits are implemented in the vibronic states of I 2 , while gate operations are realized by optimally designed laser pulses. The methodological aspects of the simulation are discussed in detail. We show that the algorithm for solving a gate pulse-design problem has the same mathematical form as a state-to-state control problem in the density matrix formalism, which provides monotonically convergent algorithms as an alternative to the Krotov method. The sequential irradiation of separately designed gate pulses leads to the population distribution predicted by Grover's algorithm. The computational accuracy is reduced by the imperfect quality of the pulse design and by the electronic decoherence processes that are modeled by the non-Markovian master equation. However, as long as we focus on the population distribution of the vibronic qubits, we can search a target state with high probability without introducing error-correction processes during the computation. A generalized gate pulse-design scheme to explicitly include decoherence effects is outlined, in which we propose a new objective functional together with its solution algorithm that guarantees monotonic convergence.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  9. 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...

  10. 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

  11. 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.

  12. Importance of Vibronic Effects in the UV-Vis Spectrum of the 7,7,8,8-Tetracyanoquinodimethane Anion.

    Science.gov (United States)

    Tapavicza, Enrico; Furche, Filipp; Sundholm, Dage

    2016-10-11

    We present a computational method for simulating vibronic absorption spectra in the ultraviolet-visible (UV-vis) range and apply it to the 7,7,8,8-tetracyanoquinodimethane anion (TCNQ - ), which has been used as a ligand in black absorbers. Gaussian broadening of vertical electronic excitation energies of TCNQ - from linear-response time-dependent density functional theory produces only one band, which is qualitatively incorrect. Thus, the harmonic vibrational modes of the two lowest doublet states were computed, and the vibronic UV-vis spectrum was simulated using the displaced harmonic oscillator approximation, the frequency-shifted harmonic oscillator approximation, and the full Duschinsky formalism. An efficient real-time generating function method was implemented to avoid the exponential complexity of conventional Franck-Condon approaches to vibronic spectra. The obtained UV-vis spectra for TCNQ - agree well with experiment; the Duschinsky rotation is found to have only a minor effect on the spectrum. Born-Oppenheimer molecular dynamics simulations combined with calculations of the electronic excitation energies for a large number of molecular structures were also used for simulating the UV-vis spectrum. The Born-Oppenheimer molecular dynamics simulations yield a broadening of the energetically lowest peak in the absorption spectrum, but additional vibrational bands present in the experimental and simulated quantum harmonic oscillator spectra are not observed in the molecular dynamics simulations. Our results underline the importance of vibronic effects for the UV-vis spectrum of TCNQ - , and they establish an efficient method for obtaining vibronic spectra using a combination of linear-response time-dependent density functional theory and a real-time generating function approach.

  13. Resolving molecular vibronic structure using high-sensitivity two-dimensional electronic spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bizimana, Laurie A.; Brazard, Johanna; Carbery, William P.; Gellen, Tobias; Turner, Daniel B., E-mail: dturner@nyu.edu [Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003 (United States)

    2015-10-28

    Coherent multidimensional optical spectroscopy is an emerging technique for resolving structure and ultrafast dynamics of molecules, proteins, semiconductors, and other materials. A current challenge is the quality of kinetics that are examined as a function of waiting time. Inspired by noise-suppression methods of transient absorption, here we incorporate shot-by-shot acquisitions and balanced detection into coherent multidimensional optical spectroscopy. We demonstrate that implementing noise-suppression methods in two-dimensional electronic spectroscopy not only improves the quality of features in individual spectra but also increases the sensitivity to ultrafast time-dependent changes in the spectral features. Measurements on cresyl violet perchlorate are consistent with the vibronic pattern predicted by theoretical models of a highly displaced harmonic oscillator. The noise-suppression methods should benefit research into coherent electronic dynamics, and they can be adapted to multidimensional spectroscopies across the infrared and ultraviolet frequency ranges.

  14. Vibronic dephasing model for coherent-to-incoherent crossover in DNA

    Science.gov (United States)

    Karasch, Patrick; Ryndyk, Dmitry A.; Frauenheim, Thomas

    2018-05-01

    In this paper, we investigate the interplay between coherent and incoherent charge transport in cytosine-guanine (GC-) rich DNA molecules. Our objective is to introduce a physically grounded approach to dephasing in large molecules and to understand the length-dependent charge transport characteristics, and especially the crossover from the coherent tunneling to incoherent hopping regime at different temperatures. Therefore, we apply the vibronic dephasing model and compare the results to the Büttiker probe model which is commonly used to describe decoherence effects in charge transport. Using the full ladder model and simplified one-dimensional model of DNA, we consider molecular junctions with alternating and stacked GC sequences and compare our results to recent experimental measurements.

  15. Two Schemes for Generation of Entanglement for Vibronic Collective States of Multiple Trapped Ions

    International Nuclear Information System (INIS)

    Yang Wenxing; Li Jiahua; Zheng Anshou

    2007-01-01

    We propose two schemes to prepare entanglement for the vibronic collective states of multiple trapped ions. The first scheme aims to generating multipartite entanglement for vibrational modes of trapped ions, which only requires a single laser beam tuned to the ionic carrier frequency. Our scheme works in the mediated excitation regime, in which the corresponding Rabi frequency is equal to the trap frequency. Beyond their fundamental importance, these states may be of interest for experimental studies on decoherence since the present scheme operates in a fast way. The second scheme aims to preparing the continuous variable multimode maximally Greenberger-Horne-Zeilinger state. The distinct advantage is that the operation time is only limited by the available laser intensity, not by the inherent mechanisms such as off-resonant excitations. This makes it promising to obtain entanglement of multiple coherent and squeezing states with desired amplitudes in a reasonable time.

  16. Intermolecular dynamics studied by paramagnetic tagging

    Energy Technology Data Exchange (ETDEWEB)

    Xu Xingfu; Keizers, Peter H. J. [Leiden University, Institute of Chemistry (Netherlands); Reinle, Wolfgang; Hannemann, Frank; Bernhardt, Rita [Universitaet des Saarlandes, Naturwissenschaftlich-Technische Fakultaet III, Institut fuer Biochemie (Germany); Ubbink, Marcellus [Leiden University, Institute of Chemistry (Netherlands)], E-mail: m.ubbink@chem.leidenuniv.nl

    2009-04-15

    Yeast cytochrome c and bovine adrenodoxin form a dynamic electron transfer complex, which is a pure encounter complex. It is demonstrated that the dynamic nature of the interaction can readily be probed by using a rigid lanthanide tag attached to cytochrome c. The tag, Caged Lanthanide NMR Probe 5, induces pseudocontact shifts and residual dipolar couplings and does not perturb the binding interface. Due to the dynamics in the complex, residual dipolar couplings in adrenodoxin are very small. Simulation shows that cytochrome c needs to sample a large part of the surface of adrenodoxin to explain the small degree of alignment observed for adrenodoxin. The applied method provides a simple and straightforward way to observe dynamics in protein complexes or domain-domain mobility without the need for external alignment media.

  17. Intermolecular dynamics studied by paramagnetic tagging

    International Nuclear Information System (INIS)

    Xu Xingfu; Keizers, Peter H. J.; Reinle, Wolfgang; Hannemann, Frank; Bernhardt, Rita; Ubbink, Marcellus

    2009-01-01

    Yeast cytochrome c and bovine adrenodoxin form a dynamic electron transfer complex, which is a pure encounter complex. It is demonstrated that the dynamic nature of the interaction can readily be probed by using a rigid lanthanide tag attached to cytochrome c. The tag, Caged Lanthanide NMR Probe 5, induces pseudocontact shifts and residual dipolar couplings and does not perturb the binding interface. Due to the dynamics in the complex, residual dipolar couplings in adrenodoxin are very small. Simulation shows that cytochrome c needs to sample a large part of the surface of adrenodoxin to explain the small degree of alignment observed for adrenodoxin. The applied method provides a simple and straightforward way to observe dynamics in protein complexes or domain-domain mobility without the need for external alignment media

  18. 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

  19. 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…

  20. 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.

  1. 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…

  2. Vibronic intensities for Er{sup 3+} in Cs{sub 2} NaErCl{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Acevedo, R.; Navarro, G. [Departamento de Quimica Basica, Facultad de Ciencias Fisicas y Matematicas, Universidad de Chile, Beauchef 850, Casilla 2777, Santiago (Chile); Meruane, T. [Universidad Metropolitana de Ciencias y Educacion, Av. Jose Pedro Alessandri 774, Casilla 147-C Santiago (Chile)

    2001-07-01

    In this current study, we have undertaken vibronic intensity calculations for the absorptions (({sup 4}I{sub 15/2}) {gamma}{sub k}) {yields} (({sup 4}I{sub 13/2}) {gamma}{sub l}) of the Er{sup 3+} in the Cs{sub 2}NaErCl{sub 6} elpasolite type system. This system is extremely complicated to handle from both a theoretical and an experimental viewpoints. This theoretical work shows that over an energy range of about 400 cm{sup -1}, a substantial amount of transitions are likely to take place (about 100 transitions; twenty five of them are magnetic dipole allowed and seventy five are vibronically allowed). It is then a formidable task to identify and assign all of these transitions in a non-ambiguous way. Also the experimental evidence available for these absorptions is related to a total of about twenty lines in the luminescence spectrum of this system. The spectrum itself is very challenging and the superposition of spectral features is most likely to occur. A careful analysis of the calculated vibronic intensities and overall oscillator strengths for the various transitions indicates that the current model used is both flexible and appropriate to deal with this kind of systems. In a forthcoming paper, we will examine the rather unusual high intensity associated with the (({sup 4}I{sub 15/2}) {gamma}{sub k}) {yields} (({sup 4}S{sub 3/2}) {gamma}{sub l}) excitations. (Author)

  3. Zooming in on vibronic structure by lowest-value projection reconstructed 4D coherent spectroscopy

    Science.gov (United States)

    Harel, Elad

    2018-05-01

    A fundamental goal of chemical physics is an understanding of microscopic interactions in liquids at and away from equilibrium. In principle, this microscopic information is accessible by high-order and high-dimensionality nonlinear optical measurements. Unfortunately, the time required to execute such experiments increases exponentially with the dimensionality, while the signal decreases exponentially with the order of the nonlinearity. Recently, we demonstrated a non-uniform acquisition method based on radial sampling of the time-domain signal [W. O. Hutson et al., J. Phys. Chem. Lett. 9, 1034 (2018)]. The four-dimensional spectrum was then reconstructed by filtered back-projection using an inverse Radon transform. Here, we demonstrate an alternative reconstruction method based on the statistical analysis of different back-projected spectra which results in a dramatic increase in sensitivity and at least a 100-fold increase in dynamic range compared to conventional uniform sampling and Fourier reconstruction. These results demonstrate that alternative sampling and reconstruction methods enable applications of increasingly high-order and high-dimensionality methods toward deeper insights into the vibronic structure of liquids.

  4. Quantum phase transition in the U(4) vibron model and the E(3) symmetry

    International Nuclear Information System (INIS)

    Zhang Yu; Hou Zhanfeng; Chen Huan; Wei Haiqing; Liu Yuxin

    2008-01-01

    We study the details of the U(3)-O(4) quantum phase transition in the U(4) vibron model. Both asymptotic analysis in the classical limit and rigorous calculations for finite boson number systems indicate that a second-order phase transition is still there even for the systems with boson number N ranging from tens to hundreds. Two kinds of effective order parameters, including E1 transition ratios B(E1:2 1 →1 1 )/B(E1:1 1 →0 1 ) and B(E1:0 2 →1 1 )/B(E1:1 1 →0 1 ), and the energy ratios E 2 1 /E 0 2 and E 3 1 /E 0 2 are proposed to identify the second-order phase transition in experiments. We also found that the critical point of phase transition can be approximately described by the E(3) symmetry, which persists even for moderate N∼10 protected by the scaling behaviors of quantities at the critical point. In addition, a possible empirical example exhibiting roughly the E(3) symmetry is discussed

  5. Simulation of the single-vibronic-level emission spectrum of HPS.

    Science.gov (United States)

    Mok, Daniel K W; Lee, Edmond P F; Chau, Foo-tim; Dyke, John M

    2014-05-21

    We have computed the potential energy surfaces of the X¹A' and ùA" states of HPS using the explicitly correlated multi-reference configuration interaction (MRCI-F12) method, and Franck-Condon factors between the two states, which include anharmonicity and Duschinsky rotation, with the aim of testing the assignment of the recently reported single-vibronic-level (SVL) emission spectrum of HPS [R. Grimminger, D. J. Clouthier, R. Tarroni, Z. Wang, and T. J. Sears, J. Chem. Phys. 139, 174306 (2013)]. These are the highest level calculations on these states yet reported. It is concluded that our spectral simulation supports the assignments of the molecular carrier, the electronic states involved and the vibrational structure of the experimental laser induced fluorescence, and SVL emission spectra proposed by Grimminger et al. [J. Chem. Phys. 139, 174306 (2013)]. However, there remain questions unanswered regarding the relative electronic energies of the two states and the geometry of the excited state of HPS.

  6. Simulation of the single-vibronic-level emission spectrum of HPS

    Energy Technology Data Exchange (ETDEWEB)

    Mok, Daniel K. W., E-mail: bcdaniel@polyu.edu.hk, E-mail: epl@soton.ac.uk; Chau, Foo-tim [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom (Hong Kong); Lee, Edmond P. F., E-mail: bcdaniel@polyu.edu.hk, E-mail: epl@soton.ac.uk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom (Hong Kong); School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom); Dyke, John M. [School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom)

    2014-05-21

    We have computed the potential energy surfaces of the X{sup ~1}A{sup ′} and A{sup ~1}A{sup ′′} states of HPS using the explicitly correlated multi-reference configuration interaction (MRCI-F12) method, and Franck–Condon factors between the two states, which include anharmonicity and Duschinsky rotation, with the aim of testing the assignment of the recently reported single-vibronic-level (SVL) emission spectrum of HPS [R. Grimminger, D. J. Clouthier, R. Tarroni, Z. Wang, and T. J. Sears, J. Chem. Phys. 139, 174306 (2013)]. These are the highest level calculations on these states yet reported. It is concluded that our spectral simulation supports the assignments of the molecular carrier, the electronic states involved and the vibrational structure of the experimental laser induced fluorescence, and SVL emission spectra proposed by Grimminger et al. [J. Chem. Phys. 139, 174306 (2013)]. However, there remain questions unanswered regarding the relative electronic energies of the two states and the geometry of the excited state of HPS.

  7. Simulation of the single-vibronic-level emission spectrum of HPS

    International Nuclear Information System (INIS)

    Mok, Daniel K. W.; Chau, Foo-tim; Lee, Edmond P. F.; Dyke, John M.

    2014-01-01

    We have computed the potential energy surfaces of the X ~1 A ′ and A ~1 A ′′ states of HPS using the explicitly correlated multi-reference configuration interaction (MRCI-F12) method, and Franck–Condon factors between the two states, which include anharmonicity and Duschinsky rotation, with the aim of testing the assignment of the recently reported single-vibronic-level (SVL) emission spectrum of HPS [R. Grimminger, D. J. Clouthier, R. Tarroni, Z. Wang, and T. J. Sears, J. Chem. Phys. 139, 174306 (2013)]. These are the highest level calculations on these states yet reported. It is concluded that our spectral simulation supports the assignments of the molecular carrier, the electronic states involved and the vibrational structure of the experimental laser induced fluorescence, and SVL emission spectra proposed by Grimminger et al. [J. Chem. Phys. 139, 174306 (2013)]. However, there remain questions unanswered regarding the relative electronic energies of the two states and the geometry of the excited state of HPS

  8. Effect of isotopic substitution on the collisional quenching of vibronically excited CO+

    International Nuclear Information System (INIS)

    Katayama, D.H.; Welsh, J.A.

    1983-01-01

    Rovibronic levels of the A 2 Pi/sub i/ state for 12 C 16 O + and 13 C 16 O + have been selectively excited by a pulsed, tunable dye laser and their time resolved fluorescence obtained as a function of helium pressure. These ions are formed by reaction of neutral carbon monoxide with helium metastable atoms created in a dc discharge. Since 13 CO + has essentially the same potential energy curves as 12 CO + , but differs primarily in its vibrational energy spacings, this experiment accentuates the role, in the collisional deactivation process, of the high lying ground state vibrational levels which are adjacent to the laser populated vibronic levels of the A 2 Pi/sub i/ state. Quenching rates are determined for the v' = 0, 1, and 2 levels which have relatively insignificant isotope shifts of a few wave numbers for the two isotopes. The difference in rates for the two isotopic ions demonstrates the importance of the positions for the high lying v'' = 10 and 11 ground state levels which have large isotope shifts of hundreds of wave numbers. A discussion of the deactivation process is given in terms of perturbations, Franck--Condon factors, energy gaps, and other considerations

  9. Two-Dimensional Resonance Raman Signatures of Vibronic Coherence Transfer in Chemical Reactions.

    Science.gov (United States)

    Guo, Zhenkun; Molesky, Brian P; Cheshire, Thomas P; Moran, Andrew M

    2017-11-02

    Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in condensed phase systems. 2DRR spectroscopy is motivated by knowledge of non-equilibrium effects that cannot be detected with traditional resonance Raman spectroscopy. For example, 2DRR spectra may reveal correlated distributions of reactant and product geometries in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this chapter, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide. We show that signatures of "vibronic coherence transfer" in the photodissociation process can be targeted with particular 2DRR pulse sequences. Key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopy techniques are also addressed. Overall, recent experimental developments and applications of the 2DRR method suggest that it will be a valuable tool for elucidating ultrafast chemical reaction mechanisms.

  10. Ultrafast vibronic dynamics of dye molecules studied by the induced grating method

    International Nuclear Information System (INIS)

    Liu, C.H.; Troeger, P.; Laubereau, A.

    1985-08-01

    Previous work on transient polarization spectroscopy applying the induced grating technique concentrated on the time scale > 10 -11 s. Only one earlier study on a shorter time scale showed the occurrence of the so-called coherence peak without a detailed explanation for this phenomena. We report new theoretical and experimental data on a polarization effect that occurs in the nonlinear Rayleigh scattering of delayed probing pulses from induced population gratings. The periodic population changes are generated by two synchronized pumping pulses of the same frequency. Model calculations are presented, which carefully evaluate the orientational distribution and give quantitative information on the scattering signal for various polarization conditions. The scattering mechanism for the coherence peak is explained as a two step process with one photon absorption and emission process; it depends on the vibronic relaxation of the terminating level in the excited electronic state. Experimental results are reported for the vibrational and orientational relaxation times. For example values of tausub(v)=0.2+-0.2 ps and tausub(v)=0.8+-0.3 ps are measured respectively for Rhodamine 6G in ethanol and phenoxazone 9 in dioxane. Our three-beam transient grating technique under general polarization conditions can be used for the study of a variety of dynamic processes of molecules in the excited electronic or ground state. An important advantage compared to nonlinear absorption or induced dichroism techniques is that the scattering method avoids undesirable background signals. (author)

  11. A chemical approach for site-specific identification of NMR signals from protein side-chain NH{sub 3}{sup +} groups forming intermolecular ion pairs in protein–nucleic acid complexes

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kurtis M. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Nguyen, Dan; Esadze, Alexandre; Zandrashvili, Levani [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States); Gorenstein, David G. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Iwahara, Junji, E-mail: juiwahar@utmb.edu, E-mail: j.iwahara@utmb.edu [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States)

    2015-05-15

    Protein–nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein–DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH{sub 3}{sup +} groups forming the intermolecular ion pairs. A characteristic change in their {sup 1}H and {sup 15}N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain {sup 15}N and DNA phosphorodithiaote {sup 31}P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein–RNA complexes as well.

  12. A chemical approach for site-specific identification of NMR signals from protein side-chain NH3+ groups forming intermolecular ion pairs in protein–nucleic acid complexes

    International Nuclear Information System (INIS)

    Anderson, Kurtis M.; Nguyen, Dan; Esadze, Alexandre; Zandrashvili, Levani; Gorenstein, David G.; Iwahara, Junji

    2015-01-01

    Protein–nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein–DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH 3 + groups forming the intermolecular ion pairs. A characteristic change in their 1 H and 15 N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain 15 N and DNA phosphorodithiaote 31 P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein–RNA complexes as well

  13. Intermolecular cleavage by UmuD-like mutagenesis proteins

    Science.gov (United States)

    McDonald, John P.; Frank, Ekaterina G.; Levine, Arthur S.; Woodgate, Roger

    1998-01-01

    The activity of a number of proteins is regulated by self-processing reactions. Elegant examples are the cleavage of the prokaryotic LexA and λCI transcriptional repressors and the UmuD-like mutagenesis proteins. Various studies support the hypothesis that LexA and λCI cleavage reactions are predominantly intramolecular in nature. The recently described crystal structure of the Escherichia coli UmuD′ protein (the posttranslational cleavage product of the UmuD protein) suggests, however, that the region of the protein corresponding to the cleavage site is at least 50 Å away from the catalytic active site. We considered the possibility, therefore, that the UmuD-like proteins might undergo self-processing that, in contrast to LexA and λCI, occurs via an intermolecular rather than intramolecular reaction. To test this hypothesis, we introduced into E. coli compatible plasmids with mutations at either the cleavage or the catalytic site of three UmuD-like proteins. Cleavage of these proteins only occurs in the presence of both plasmids, indicating that the reaction is indeed intermolecular in nature. Furthermore, this intermolecular reaction is completely dependent upon the multifunctional RecA protein and leads to the restoration of cellular mutagenesis in nonmutable E. coli strains. Intermolecular cleavage of a biotinylated UmuD active site mutant was also observed in vitro in the presence of the wild-type UmuD′ protein, indicating that in addition to the intact UmuD protein, the normal cleavage product (UmuD′) can also act as a classical enzyme. PMID:9465040

  14. Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

    Science.gov (United States)

    Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

    2016-01-01

    An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

  15. Determination of intermolecular transfer integrals from DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Baumeier, Bjoern; Andrienko, Denis [Max-Planck Institute for Polymer Research, Mainz (Germany)

    2010-07-01

    Theoretical studies of charge transport in organic conducting systems pose a unique challenge since they require multiscale schemes that combine quantum-chemical, molecular dynamics and kinetic Monte-Carlo calculations. The description of the mobility of electrons and holes in the hopping regime relies on the determination of intermolecular hopping rates in large scale morphologies. Using Marcus theory these rates can be calculated from intermolecular transfer integrals and on-site energies. Here we present a detailed computational study on the accuracy and efficiency of density-functional theory based approaches to the determination of intermolecular transfer integrals. First, it is demonstrated how these can be obtained from quantum-chemistry calculations by forming the expectation value of a dimer Fock operator with frontier orbitals of two neighboring monomers based on a projective approach. We then consider the prototypical example of one pair out of a larger morphology of Tris(8-hydroxyquinolinato)aluminium (Alq3) and study the influence of computational parameters, e.g. the choice of basis sets, exchange-correlation functional, and convergence criteria, on the calculated transfer integrals. The respective accuracies and efficiencies are compared in order to derive an optimal strategy for future simulations based on the full morphology.

  16. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    Directory of Open Access Journals (Sweden)

    Peter I. Nagy

    2014-10-01

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

  17. 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...... interaction-induced binary chemical shift d, the anisotropy of the shielding tensor ?s, and the NQC constant along the internuclear axis ?ll are calculated as a function of the internuclear distance. DHF shielding calculations are carried out using gauge-including atomic orbitals. For comparison, the full...... is obtained for d and ?s in Xe2. For these properties, the currently most complete theoretical description is obtained by a piecewise approximation where the uncorrelated relativistic DHF results obtained close to the basis-set limit are corrected, on the one hand, for NR correlation effects and, on the other...

  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. 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.

  20. 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.

  1. Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

    International Nuclear Information System (INIS)

    Ye, ChuanXiang; Zhao, Yi; Liang, WanZhen

    2015-01-01

    The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT

  2. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    Directory of Open Access Journals (Sweden)

    Venkatesha R. Hathwar

    2015-09-01

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

  3. 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

  4. 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

  5. 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)

  6. Symmetry in the polarization expansion for intermolecular forces

    International Nuclear Information System (INIS)

    Chipman, D.M.; Hirschfelder, J.O.

    1980-01-01

    In the usual polarization expansion for intermolecular forces, exchange effects that determine the separations of energy levels within the manifold of interacting states are ignored. Previous low order calculations on simple physical systems have indicated that these exchange terms can be described reasonably well by an appropriate ad hoc symmetrization of the polarization wave function (the SYM-P method). But theoretical considerations suggest that the SYM-P method should be good for only one of the interacting states and not for the others in the manifold. Here this long standing apparent conflict between theoretical expectations and actual results is explained by consideration of a simple model system in which the relevant equations can be solved exactly. It is concluded that while the SYM-P method is potentially exact for only one of the interacting states, it may provide good approximations to the other states of the manifold in the case of large separations of the interacting subsystems

  7. Testing intermolecular potential functions using transport property data

    International Nuclear Information System (INIS)

    Clifford, A.A.; Dickinson, E.; Gray, P.; Scott, A.C.

    1975-01-01

    The viscosity of hydrogen has been measured at eight temperatures from 273 to 1060K, using a capillary-flow viscometer. The results have been used to test the repulsive part of a recently formulated H 2 /H 2 intermolecular potential function, obtained from molecular-beam measurements. Agreement between the experimental and predicted values for viscosity is within 3.5%, which corresponds approximately to the combined quoted uncertainties in the two sets of data. However, if the value of the distance parameter of the potential is reduced by about 1.5%, the agreement obtained is within 0.75% over the whole temperature range. This modified potential function gives better agreement with the available higher temperature viscosities and second virial coefficients. (author)

  8. On the Magnitude of the Nonadiabatic Error for Highly Coupled Radicals

    Science.gov (United States)

    Stanton, J. F.

    2009-06-01

    A review is given of recent advances in the construction of (quasi)diabatic model Hamiltonians and their application to analyzing the spectroscopy of molecules with strong vibronic coupling. A numerical application to the vibronic levels of the BNB radical below 0.6 eV is presented, together with corresponding adiabatic (quantum chemistry) calculations. The agreement with the experimental levels is nearly quantitative with the model Hamiltonian, attesting to the power of the approach. On the contrary, it is also revealed that the magnitude of the nonadiabatic contributions to the zero-point energy and the lowest fundamental frequency of the coupling mode are considerably larger than expected, at least by your narrator.

  9. Coupling effect on the electronic transport through dimolecular junctions

    International Nuclear Information System (INIS)

    Long, Meng-Qiu; Wang, Lingling; Chen, Ke-Qiu; Li, Xiao-Fei; Zou, B.S.; Shuai, Z.

    2007-01-01

    Using nonequilibrium Green's function and first-principle calculations, we investigate the transport behaviors of a dimolecule device with two 1,4-Dithiolbenzenes (DTB) sandwiched between two gold electrodes. The results show that the intermolecular coupling effect plays an important role in the conducting behavior of the system. By changing the dihedral angles between the two DTB molecules, namely changing the magnitude of the intermolecular interaction, a different transport behavior can be observed in the system

  10. Systematic study on intermolecular valence-band dispersion in molecular crystalline films

    International Nuclear Information System (INIS)

    Yamane, Hiroyuki; Kosugi, Nobuhiro

    2015-01-01

    Highlights: • Intermolecular valence-band dispersion of crystalline films of phthalocyanines. • Intermolecular transfer integral versus lattice constant. • Site-specific intermolecular interaction and resultant valence-band dispersion. • Band narrowing effect induced by elevated temperature. - Abstract: Functionalities of organic semiconductors are governed not only by individual properties of constituent molecules but also by solid-state electronic states near the Fermi level such as frontier molecular orbitals, depending on weak intermolecular interactions in various conformations. The individual molecular property has been widely investigated in detail; on the other hand, the weak intermolecular interaction is difficult to investigate precisely due to the presence of the structural and thermal energy broadenings in organic solids. Here we show quite small but essential intermolecular valence band dispersions and their temperature dependence of sub-0.1-eV scale in crystalline films of metal phthalocyanines (H_2Pc, ZnPc, CoPc, MnPc, and F_1_6ZnPc) by using angle-resolved photoemission spectroscopy (ARPES) with synchrotron radiation. The observed bands show intermolecular and site dependent dispersion widths, phases, and periodicities, for different chemical substitution of terminal groups and central metals in the phthalocyanine molecule. The precise and systematic band-dispersion measurement would be a credible approach toward the comprehensive understanding of intermolecular interactions and resultant charge transport properties as well as their tuning by substituents in organic molecular systems.

  11. Intense Vibronic Modulation of the Chiral Photoelectron Angular Distribution Generated by Photoionization of Limonene Enantiomers with Circularly Polarized Synchrotron Radiation.

    Science.gov (United States)

    Rafiee Fanood, Mohammad M; Ganjitabar, Hassan; Garcia, Gustavo A; Nahon, Laurent; Turchini, Stefano; Powis, Ivan

    2018-04-17

    Photoionization of the chiral monoterpene limonene has been investigated using polarized synchrotron radiation between the adiabatic ionization threshold, 8.505 and 23.5 eV. A rich vibrational structure is seen in the threshold photoelectron spectrum and is interpreted using a variety of computational methods. The corresponding photoelectron circular dichroism-measured in the photoelectron angular distribution as a forward-backward asymmetry with respect to the photon direction-was found to be strongly dependent on the vibronic structure appearing in the photoelectron spectra, with the observed asymmetry even switching direction in between the major vibrational peaks. This effect can be ultimately attributed to the sensitivity of this dichroism to small phase shifts between adjacent partial waves of the outgoing photoelectron. These observations have implications for potential applications of this chiroptical technique, where the enantioselective analysis of monoterpene components is of particular interest. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Vibronic interactions proceeding from combined analytical and numerical considerations: Covalent functionalization of graphene by benzene, distortions, electronic transitions

    Energy Technology Data Exchange (ETDEWEB)

    Krasnenko, V.; Boltrushko, V.; Hizhnyakov, V. [Institute of Physics, University of Tartu, W. Ostwaldi Str 1, 50411 Tartu (Estonia)

    2016-04-07

    Chemically bound states of benzene molecules with graphene are studied both analytically and numerically. The states are formed by switching off intrabonds of π-electrons in C{sub 6} rings to interbonds. A number of different undistorted and distorted structures are established both with aligned and with transversal mutual orientation of benzene and graphene. The vibronic interactions causing distortions of bound states are found, by using a combination of analytical and numerical considerations. This allows one to determine all electronic transitions of π-electrons without explicit numerical calculations of excited states, to find the conical intersections of potentials, and to show that the mechanism of distortions is the pseudo-Jahn-Teller effect. It is found that the aligned distorted benzene molecule placed between two graphene sheets makes a chemical bond with both of them, which may be used for fastening of graphene sheets together.

  13. Structural variability and the nature of intermolecular interactions in Watson-Crick B-DNA base pairs.

    Science.gov (United States)

    Czyznikowska, Z; Góra, R W; Zaleśny, R; Lipkowski, P; Jarzembska, K N; Dominiak, P M; Leszczynski, J

    2010-07-29

    A set of nearly 100 crystallographic structures was analyzed using ab initio methods in order to verify the effect of the conformational variability of Watson-Crick guanine-cytosine and adenine-thymine base pairs on the intermolecular interaction energy and its components. Furthermore, for the representative structures, a potential energy scan of the structural parameters describing mutual orientation of the base pairs was carried out. The results were obtained using the hybrid variational-perturbational interaction energy decomposition scheme. The electron correlation effects were estimated by means of the second-order Møller-Plesset perturbation theory and coupled clusters with singles and doubles method adopting AUG-cc-pVDZ basis set. Moreover, the characteristics of hydrogen bonds in complexes, mimicking those appearing in B-DNA, were evaluated using topological analysis of the electron density. Although the first-order electrostatic energy is usually the largest stabilizing component, it is canceled out by the associated exchange repulsion in majority of the studied crystallographic structures. Therefore, the analyzed complexes of the nucleic acid bases appeared to be stabilized mainly by the delocalization component of the intermolecular interaction energy which, in terms of symmetry adapted perturbation theory, encompasses the second- and higher-order induction and exchange-induction terms. Furthermore, it was found that the dispersion contribution, albeit much smaller in terms of magnitude, is also a vital stabilizing factor. It was also revealed that the intermolecular interaction energy and its components are strongly influenced by four (out of six) structural parameters describing mutual orientation of bases in Watson-Crick pairs, namely shear, stagger, stretch, and opening. Finally, as a part of a model study, much of the effort was devoted to an extensive testing of the UBDB databank. It was shown that the databank quite successfully reproduces the

  14. Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

    Science.gov (United States)

    Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

    2011-03-24

    The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

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

    International Nuclear Information System (INIS)

    Hormain, Laureline; Monnerville, Maurice; Toubin, Céline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stéphane; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón

    2015-01-01

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

  16. 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).

  17. 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...... little effect on HGly-GlyEHEGly--Gly. This contrasts with our earlier studies on 1P–S–H2O in that Na+, F− and Cl− are found as hydration centers from the induced changes on HIP-IPEHEIP--IP in the presence of S, while Br−, I−, and SCN− are found to act as hydrophiles. In comparison with the Hofmeister...... ranking of these ions, the kosmotropes are hydration centers and the more kosmotropic the higher the hydration number, consistent with the original Hofmeister’s concept of “H2O withdrawing power.” Br−, I− and SCN−, on the other hand, acted as hydrophiles and the more chaotropic they are the more...

  18. Localized-overlap approach to calculations of intermolecular interactions

    Science.gov (United States)

    Rob, Fazle

    Symmetry-adapted perturbation theory (SAPT) based on the density functional theory (DFT) description of the monomers [SAPT(DFT)] is one of the most robust tools for computing intermolecular interaction energies. Currently, one can use the SAPT(DFT) method to calculate interaction energies of dimers consisting of about a hundred atoms. To remove the methodological and technical limits and extend the size of the systems that can be calculated with the method, a novel approach has been proposed that redefines the electron densities and polarizabilities in a localized way. In the new method, accurate but computationally expensive quantum-chemical calculations are only applied for the regions where it is necessary and for other regions, where overlap effects of the wave functions are negligible, inexpensive asymptotic techniques are used. Unlike other hybrid methods, this new approach is mathematically rigorous. The main benefit of this method is that with the increasing size of the system the calculation scales linearly and, therefore, this approach will be denoted as local-overlap SAPT(DFT) or LSAPT(DFT). As a byproduct of developing LSAPT(DFT), some important problems concerning distributed molecular response, in particular, the unphysical charge-flow terms were eliminated. Additionally, to illustrate the capabilities of SAPT(DFT), a potential energy function has been developed for an energetic molecular crystal of 1,1-diamino-2,2-dinitroethylene (FOX-7), where an excellent agreement with the experimental data has been found.

  19. 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.

  20. Effect of donor orientation on ultrafast intermolecular electron transfer in coumarin-amine systems

    International Nuclear Information System (INIS)

    Singh, P. K.; Nath, S.; Bhasikuttan, A. C.; Kumbhakar, M.; Mohanty, J.; Sarkar, S. K.; Mukherjee, T.; Pal, H.

    2008-01-01

    Effect of donor amine orientation on nondiffusive ultrafast intermolecular electron transfer (ET) reactions in coumarin-amine systems has been investigated using femtosecond fluorescence upconversion measurements. Intermolecular ET from different aromatic and aliphatic amines used as donor solvents to the excited coumarin-151 (C151) acceptor occurs with ultrafast rates such that the shortest fluorescence lifetime component (τ 1 ) is the measure of the fastest ET rate (τ 1 =τ ET fast =(k ET fast ) -1 ), assigned to the C151-amine contact pairs in which amine donors are properly oriented with respect to C151 to maximize the acceptor-donor electronic coupling (V el ). It is interestingly observed that as the amine solvents are diluted by suitable diluents (either keeping solvent dielectric constant similar or with increasing dielectric constant), the τ 1 remains almost in the similar range as long as the amine dilution does not cross a certain critical limit, which in terms of the amine mole fraction (x A ) is found to be ∼0.4 for aromatic amines and ∼0.8 for aliphatic amines. Beyond these dilutions in the two respective cases of the amine systems, the τ 1 values are seen to increase very sharply. The large difference in the critical x A values involving aromatic and aliphatic amine donors has been rationalized in terms of the largely different orientational restrictions for the ET reactions as imposed by the aliphatic (n-type) and aromatic (π-type) nature of the amine donors [A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008)]. Since the highest occupied molecular orbital (HOMO) of the n-type aliphatic amines is mostly centralized at the amino nitrogen, only some specific orientations of these amines with respect to the close-contact acceptor dye [also of π-character; A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008) and E. W. Castner et al., J. Phys. Chem. A 104, 2869 (2000)] can give suitable V el and thus ultrafast ET reaction. In contrary, the

  1. Orientation correlation and intermolecular structure of GeCl4, VCl4 and other tetrachloride liquids

    International Nuclear Information System (INIS)

    Nath, P.P.; Sarkar, S.; Joarder, R.N.

    2007-01-01

    The intermolecular structure and correlation of GeCl 4 , VCl 4 and other tetrachloride liquids can be well described by Misawa's orientation correlation model originally applied to liquid CCl 4 . The model supports on average a specific 'corner' to 'face' correlation, but evidently very different from 'Apollo' type model. The Misawa model appears to work, in some respect, even better than reference interaction site model (RISM) used for long to describe intermolecular structure of such molecular systems. The test and comparison are made through the calculation of small asymmetric part of the intermolecular structure and evaluation of partial atom-atom distribution functions

  2. The shape of the electronic circular dichroism spectrum of (2,6-dimethylphenyl)(phenyl)methanol: interplay between conformational equilibria and vibronic effects.

    Science.gov (United States)

    Padula, Daniele; Cerezo, Javier; Pescitelli, Gennaro; Santoro, Fabrizio

    2017-12-13

    Comparison between chiroptical spectra and theoretical predictions is the method of choice for the assignment of the absolute configuration of chiral compounds in solution. Here we report the case of an apparently simple biarylcarbinol, whose electronic circular dichroism (ECD) in the 1 L b region exhibits a peculiar alternation of negative and positive bands. Adopting Density Functional Theory, and describing solvent effects with implicit methods, we found three stable conformers in ethanol, each of them with two close lying states corresponding to similar local 1 L b excitations on the two phenyls. We computed the corresponding vibronic ECD spectra in harmonic approximation, including Duschinsky mixings as well as both Franck Condon (FC) and Herzberg Teller (HT) effects. Exploiting a recently developed mixed quantum/classical method, we further investigated the contribution of the vibronic spectra of out-of-equilibrium structures along the interconversion path connecting the different conformers. In this way, we achieved a reasonable agreement with experiment and attributed the alternating signs of the bands to the existence of different conformers. The remaining discrepancies with experiment indicate that specific solute-solvent interactions modulate the relative conformers' stabilities, calling for new methods able to combine Molecular Dynamics explorations and vibronic calculations. Moreover, the poor performance of HT approaches and the existence of two closely-lying states suggest the necessity of an improved fully-nonadiabatic vibronic approach. These findings demonstrate that even for such a simple system as the biarylcarbinol investigated here, a full reproduction of the fine details of the ECD spectrum requires the development of new improved methods.

  3. Contrasts between the vibronic contributions in the tris-(2,2'-bipyridyl)osmium(II) emission spectrum and the implications of resonance-Raman parameters.

    Science.gov (United States)

    Ondongo, Onduru S; Endicott, John F

    2009-04-06

    The emission spectrum of the tris-(2,2'-bipyridine)osmium(II) metal-to-ligand charge transfer (MLCT) excited-state frozen solution at 77 K differs qualitatively from that expected based on its reported resonance-Raman (rR) parameters in that (1) the dominant vibronic contributions to the emission spectrum are in the low frequency regime (corresponding to nuclear displacements in largely to metal-ligand vibrational modes) and these contributions are negligible in the rR; and (2) the amplitude of the emission sideband components that correspond to envelopes of largely bpy centered vibrational modes is about 40% of that expected (relative to the amplitude observed for the band origin) for a simple vibronic progression in these modes. The distortions in low frequency vibrational modes are attributable to configurational mixing between metal centered (LF) and MLCT excited states, and the small amplitudes of the bpy-mode vibronic components may be a consequence of some intrinsic differences of the distortions of the (3)MLCT and (1)MLCT excited states such as the zero-field splitting of the (3)MLCT excited state and the different distortions of these excited-state components.

  4. Interplay between intramolecular and intermolecular structures of 1,1,2,2-tetrachloro-1,2-difluoroethane

    Science.gov (United States)

    Rovira-Esteva, M.; Murugan, N. A.; Pardo, L. C.; Busch, S.; Tamarit, J. Ll.; Pothoczki, Sz.; Cuello, G. J.; Bermejo, F. J.

    2011-08-01

    We report on the interplay between the short-range order of molecules in the liquid phase of 1,1,2,2-tetrachloro-1,2-difluoroethane and the possible molecular conformations, trans and gauche. Two complementary approaches have been used to get a comprehensive picture: analysis of neutron-diffraction data by a Bayesian fit algorithm and a molecular dynamics simulation. The results of both show that the population of trans and gauche conformers in the liquid state can only correspond to the gauche conformer being more stable than the trans conformer. Distinct conformer geometries induce distinct molecular short-range orders around them, suggesting that a deep intra- and intermolecular interaction coupling is energetically favoring one of the conformers by reducing the total molecular free energy.

  5. 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

  6. Exciplex: An Intermolecular Charge-Transfer Approach for TADF.

    Science.gov (United States)

    Sarma, Monima; Wong, Ken-Tsung

    2018-04-03

    Organic materials that display thermally activated delayed fluorescence (TADF) are a striking class of functional materials that have witnessed a booming progress in recent years. In addition to pure TADF emitters achieved by the subtle manipulations of intramolecular charge transfer processes with sophisticated molecular structures, a new class of efficient TADF-based OLEDs with emitting layer formed by blending electron donor and acceptor molecules that involve intermolecular charge transfer have also been fabricated. In contrast to pure TADF materials, the exciplex-based systems can realize small ΔEST (0-0.05 eV) much more easily since the electron and hole are positioned on two different molecules, thereby giving small exchange energy. Consequently, exciplex-based OLEDs have the prospective to maximize the TADF contribution and achieve theoretical 100% internal quantum efficiency. Therefore, the challenging issue of achieving small ΔEST in organic systems could be solved. In this article, we summarize and discuss the latest and most significant developments regarding these rapidly evolving functional materials, wherein the majority of the reported exciplex forming systems are categorized into two sub-groups, viz. (a) exciplex as TADF emitters and (b) those as hosts for fluorescent, phosphorescent and TADF dopants according to their structural features and applications. The working mechanisms of the direct electroluminescence from the donor/acceptor interface and the exciplex-forming systems as co-host for the realization of high efficiency OLEDs are reviewed and discussed. This article delivers a summary of the current progresses and achievements of exciplex-based researches and points out the future challenges to trigger more research endeavors to this growing field.

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

    International Nuclear Information System (INIS)

    Zheng, Rui; Zheng, Limin; Yang, Minghui; Lu, Yunpeng

    2015-01-01

    Theoretical studies of the potential energy surface (PES) and bound states are performed for the N 2 –N 2 O van der Waals (vdW) complex. A four-dimensional intermolecular PES is constructed at the level of single and double excitation coupled-cluster method with a non-iterative perturbation treatment of triple excitations [CCSD(T)] with aug-cc-pVTZ basis set supplemented with bond functions. Two equivalent T-shaped global minima are located, in which the O atom of N 2 O monomer is near the N 2 monomer. The intermolecular fundamental vibrational states are assigned by inspecting the orientation of the nodal surface of the wavefunctions. The calculated frequency for intermolecular disrotation mode is 23.086 cm −1 , which is in good agreement with the available experimental data of 22.334 cm −1 . A negligible tunneling splitting with the value of 4.2 MHz is determined for the ground vibrational state and the tunneling splitting increases as the increment of the vibrational frequencies. Rotational levels and transition frequencies are calculated for both isotopomers 14 N 2 –N 2 O and 15 N 2 –N 2 O. The accuracy of the PES is validated by the good agreement between theoretical and experimental results for the transition frequencies and spectroscopic parameters

  8. 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.

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

    Science.gov (United States)

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

    2007-10-28

    Relativistic effects on the (129)Xe nuclear magnetic resonance shielding and (131)Xe nuclear quadrupole coupling (NQC) tensors are examined in the weakly bound Xe(2) system at different levels of theory including the relativistic four-component Dirac-Hartree-Fock (DHF) method. The intermolecular interaction-induced binary chemical shift delta, the anisotropy of the shielding tensor Deltasigma, and the NQC constant along the internuclear axis chi( parallel) are calculated as a function of the internuclear distance. DHF shielding calculations are carried out using gauge-including atomic orbitals. For comparison, the full leading-order one-electron Breit-Pauli perturbation theory (BPPT) is applied using a common gauge origin. Electron correlation effects are studied at the nonrelativistic (NR) coupled-cluster singles and doubles with perturbational triples [CCSD(T)] level of theory. The fully relativistic second-order Moller-Plesset many-body perturbation (DMP2) theory is used to examine the cross coupling between correlation and relativity on NQC. The same is investigated for delta and Deltasigma by BPPT with a density functional theory model. A semiquantitative agreement between the BPPT and DHF binary property curves is obtained for delta and Deltasigma in Xe(2). For these properties, the currently most complete theoretical description is obtained by a piecewise approximation where the uncorrelated relativistic DHF results obtained close to the basis-set limit are corrected, on the one hand, for NR correlation effects and, on the other hand, for the BPPT-based cross coupling of relativity and correlation. For chi( parallel), the fully relativistic DMP2 results obtain a correction for NR correlation effects beyond MP2. The computed temperature dependence of the second virial coefficient of the (129)Xe nuclear shielding is compared to experiment in Xe gas. Our best results, obtained with the piecewise approximation for the binary chemical shift combined with the

  10. 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.

  11. Enhanced vibronic interaction caused by local lattice symmetry lowering in the (Fe, Mg)As2 ternary system

    Science.gov (United States)

    Pishtshev, A.; Rubin, P.

    2018-04-01

    By means of periodic density functional theory (DFT) electronic structure calculations, we investigate iron-site doping effects in a structural model of bulk FeAs2. Simulations performed within the projector augmented-wave method-Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) functional scheme reveal that the impacts of the two stoichiometric substitutions Fe → Mg and Fe → Ni are radically different with respect to the structural and electronic behavior of the dopants. In particular, unlike the Ni dopant, the Mg dopant incorporated in FeAs2 occupies a noncentral equilibrium position characterized by an off-center displacement from the reference higher-symmetry position. Analysis of the respective electron and vibrational factors allows us to explain this result in terms of the local pseudo Jahn-Teller effect (pJTE). On the basis of DFT calculations, we deduce which electron orbitals and lattice vibrational modes are appropriate for promoting the local instability at the origin of the pJTE. Quantitative evaluations of the pJTE parameters performed within the polyatomic formalism of an effective tight-binding model show that it is just the enhanced vibronic interaction in the Mg-[FeAs6] cluster that is responsible for the local lattice symmetry breaking.

  12. 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

  13. Molecular dynamics simulation of nonlinear spectroscopies of intermolecular motions in liquid water.

    Science.gov (United States)

    Yagasaki, Takuma; Saito, Shinji

    2009-09-15

    Water is the most extensively studied of liquids because of both its ubiquity and its anomalous thermodynamic and dynamic properties. The properties of water are dominated by hydrogen bonds and hydrogen bond network rearrangements. Fundamental information on the dynamics of liquid water has been provided by linear infrared (IR), Raman, and neutron-scattering experiments; molecular dynamics simulations have also provided insights. Recently developed higher-order nonlinear spectroscopies open new windows into the study of the hydrogen bond dynamics of liquid water. For example, the vibrational lifetimes of stretches and a bend, intramolecular features of water dynamics, can be accurately measured and are found to be on the femtosecond time scale at room temperature. Higher-order nonlinear spectroscopy is expressed by a multitime correlation function, whereas traditional linear spectroscopy is given by a one-time correlation function. Thus, nonlinear spectroscopy yields more detailed information on the dynamics of condensed media than linear spectroscopy. In this Account, we describe the theoretical background and methods for calculating higher order nonlinear spectroscopy; equilibrium and nonequilibrium molecular dynamics simulations, and a combination of both, are used. We also present the intermolecular dynamics of liquid water revealed by fifth-order two-dimensional (2D) Raman spectroscopy and third-order IR spectroscopy. 2D Raman spectroscopy is sensitive to couplings between modes; the calculated 2D Raman signal of liquid water shows large anharmonicity in the translational motion and strong coupling between the translational and librational motions. Third-order IR spectroscopy makes it possible to examine the time-dependent couplings. The 2D IR spectra and three-pulse photon echo peak shift show the fast frequency modulation of the librational motion. A significant effect of the translational motion on the fast frequency modulation of the librational motion is

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

    Science.gov (United States)

    Wang, Yi-Siang; Yin, Chih-Chien; Chao, Sheng D

    2014-10-07

    We perform an ab initio computational study of molecular complexes with the general formula CF3X-B that involve one trifluorohalomethane CF3X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH3 and PH3), two n-pairs (H2O and H2S), two n-pairs with an unsaturated bond (H2CO and H2CS), and a single π-pair (C2H4) and two π-pairs (C2H2). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the σ-hole model. Upon formation of stable complexes, the C-X bond lengths shorten, while the C-X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the σ-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.

  15. Intermolecular interactions in the condensed phase: Evaluation of semi-empirical quantum mechanical methods.

    Science.gov (United States)

    Christensen, Anders S; Kromann, Jimmy C; Jensen, Jan H; Cui, Qiang

    2017-10-28

    To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy in solution is computed via a thermodynamic cycle that integrates dimer binding energy in the gas phase at the coupled cluster level and solute-solvent interaction with density functional theory; the estimated uncertainty of such calculated interaction energy is ±1.5 kcal/mol. The dataset is used to benchmark the performance of a set of semi-empirical quantum mechanical (SQM) methods that include DFTB3-D3, DFTB3/CPE-D3, OM2-D3, PM6-D3, PM6-D3H+, and PM7 as well as the HF-3c method. We find that while all tested SQM methods tend to underestimate binding energies in the gas phase with a root-mean-squared error (RMSE) of 2-5 kcal/mol, they overestimate binding energies in the solution phase with an RMSE of 3-4 kcal/mol, with the exception of DFTB3/CPE-D3 and OM2-D3, for which the systematic deviation is less pronounced. In addition, we find that HF-3c systematically overestimates binding energies in both gas and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need to be treated in a balanced fashion.

  16. Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy

    International Nuclear Information System (INIS)

    Mani, Tomoyasu; Brookhaven National Laboratory; Grills, David C.

    2017-01-01

    Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we show that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1 . IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.

  17. Intermolecular interactions in the condensed phase: Evaluation of semi-empirical quantum mechanical methods

    Science.gov (United States)

    Christensen, Anders S.; Kromann, Jimmy C.; Jensen, Jan H.; Cui, Qiang

    2017-10-01

    To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy in solution is computed via a thermodynamic cycle that integrates dimer binding energy in the gas phase at the coupled cluster level and solute-solvent interaction with density functional theory; the estimated uncertainty of such calculated interaction energy is ±1.5 kcal/mol. The dataset is used to benchmark the performance of a set of semi-empirical quantum mechanical (SQM) methods that include DFTB3-D3, DFTB3/CPE-D3, OM2-D3, PM6-D3, PM6-D3H+, and PM7 as well as the HF-3c method. We find that while all tested SQM methods tend to underestimate binding energies in the gas phase with a root-mean-squared error (RMSE) of 2-5 kcal/mol, they overestimate binding energies in the solution phase with an RMSE of 3-4 kcal/mol, with the exception of DFTB3/CPE-D3 and OM2-D3, for which the systematic deviation is less pronounced. In addition, we find that HF-3c systematically overestimates binding energies in both gas and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need to be treated in a balanced fashion.

  18. Complete relaxation and conformational exchange matrix (CORCEMA) analysis of intermolecular saturation transfer effects in reversibly forming ligand-receptor complexes.

    Science.gov (United States)

    Jayalakshmi, V; Krishna, N Rama

    2002-03-01

    A couple of recent applications of intermolecular NOE (INOE) experiments as applied to biomolecular systems involve the (i) saturation transfer difference NMR (STD-NMR) method and (ii) the intermolecular cross-saturation NMR (ICS-NMR) experiment. STD-NMR is a promising tool for rapid screening of a large library of compounds to identify bioactive ligands binding to a target protein. Additionally, it is also useful in mapping the binding epitopes presented by a bioactive ligand to its target protein. In this latter application, the STD-NMR technique is essentially similar to the ICS-NMR experiment, which is used to map protein-protein or protein-nucleic acid contact surfaces in complexes. In this work, we present a complete relaxation and conformational exchange matrix (CORCEMA) theory (H. N. B. Moseley et al., J. Magn. Reson. B 108, 243-261 (1995)) applicable for these two closely related experiments. As in our previous work, we show that when exchange is fast on the relaxation rate scale, a simplified CORCEMA theory can be formulated using a generalized average relaxation rate matrix. Its range of validity is established by comparing its predictions with those of the exact CORCEMA theory which is valid for all exchange rates. Using some ideal model systems we have analyzed the factors that influence the ligand proton intensity changes when the resonances from some protons on the receptor protein are saturated. The results show that the intensity changes in the ligand signals in an intermolecular NOE experiment are very much dependent upon: (1) the saturation time, (2) the location of the saturated receptor protons with respect to the ligand protons, (3) the conformation of the ligand-receptor interface, (4) the rotational correlation times for the molecular species, (5) the kinetics of the reversibly forming complex, and (6) the ligand/receptor ratio. As an example of a typical application of the STD-NMR experiment we have also simulated the STD effects for a

  19. Resonant exciton-phonon coupling in ZnO nanorods at room temperature

    Directory of Open Access Journals (Sweden)

    Soumee Chakraborty

    2011-09-01

    Full Text Available Vibronic and optoelectronic properties, along with detailed studies of exciton-phonon coupling at room temperature (RT for random and aligned ZnO nanorods are reported. Excitation energy dependent Raman studies are performed for detailed analysis of multi-phonon processes in the nanorods. We report here the origin of coupling between free exciton and its associated phonon replicas, including its higher order modes, in the photoluminescence spectra at RT. Resonance of excitonic electron and resonating first order zone center LO phonon, invoked strongly by Frolich interaction, are made responsible for the observed phenomenon.

  20. 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

  1. 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 ...

  2. Molecular self assembly and chiral recognition of copper octacyanophthalocyanine on Au(111): Interplay of intermolecular and molecule-substrate interactions.

    Science.gov (United States)

    Sk, Rejaul; Dhara, Barun; Miller, Joel; Deshpande, Aparna

    Submolecular resolution scanning tunneling microscopy (STM) of copper octacyanophthalocyanine, CuPc(CN)8, at 77 K demonstrates that these achiral molecules form a two dimensional (2D) tetramer-based self-assembly upon evaporation onto an atomically flat Au(111) substrate. They assemble in two different structurally chiral configurations upon adsorption on Au(111). Scanning tunneling spectroscopy (STS),acquired at 77 K, unveils the HOMO and LUMO energy levels of this self-assembly. Voltage dependent STM images show that each molecule in both the structurally chiral configurations individually becomes chiral by breaking the mirror symmetry due to the enhanced intermolecular dipolar coupling interaction at the LUMO energy while the individual molecules remain achiral at the HOMO energy and within the HOMO-LUMO gap. At the LUMO energy, the handedness of the each chiral molecule is decided by the direction of the dipolar coupling interaction in the tetramer unit cell. This preference for LUMO energy indicates that this chirality is purely electronic in nature and it manifests on top of the organizational chirality that is present in the self-assembly independent of the orbital energy. Supported by IISER Pune and DAE-BRNS, India (Project No. 2011/20/37C/17/BRNS).

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

    Science.gov (United States)

    Hellmann, Robert

    2017-03-21

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

  4. 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

  5. Salting Effects as an Illustration of the Relative Strength of Intermolecular Forces

    Science.gov (United States)

    Person, Eric C.; Golden, Donnie R.; Royce, Brenda R.

    2010-01-01

    This quick and inexpensive demonstration of the salting of an alcohol out of an aqueous solution illustrates the impact of intermolecular forces on solubility using materials familiar to many students. Ammonium sulfate (fertilizer) is added to an aqueous 35% solution of isopropyl alcohol (rubbing alcohol and water) containing food coloring as a…

  6. 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…

  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

    2013-11-28

    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.

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

    International Nuclear Information System (INIS)

    Pham Van, Tat; Deiters, Ulrich K.

    2015-01-01

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

  9. A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

    Science.gov (United States)

    Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.

    2018-02-01

    The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

  10. Complicated Fermi-type vibronic resonance: Untangling of the single-site quasi-line fluorescence excitation spectra of a methylated dibenzoporphin

    International Nuclear Information System (INIS)

    Arabei, S.M.; Kuzmitsky, V.A.; Solovyov, K.N.

    2008-01-01

    The quasi-line low-temperature (4.2 K) fluorescence excitation spectra of 2,3,12,13-tetramethyldibenzo[g,q]porphin introduced into an n-octane matrix have been measured in the range of the S 2 0 electronic transition at selective fluorescence monitoring for the two main types of impurity centers (sites). A characteristic feature of these spectra is that a conglomerate of quasi-lines - a structured complex band - is observed instead of one 0-0 quasi-line of the S 2 0 transition. In this band, the intensity distributions for the two main sites considerably differ from each other. The occurrence of such conglomerates is interpreted as a result of nonadiabatic vibrational-electronic interaction between the vibronic S 2 and S 1 states (the complex vibronic analogue of the Fermi resonance). The frequencies and intensities of individual transitions determined from the deconvolution of complex conglomerates are used as the initial data for solving the inverse spectroscopic problem: the determination of the unperturbed electronic and vibrational levels of states involved in the resonance and the vibronic-interaction matrix elements between them. This problem is solved with a method developed previously. The experimental results and their analysis are compared to the analogous data obtained earlier for meso-tetraazaporphin and meso-tetrapropylporphin. The energy intervals between the S 2 and S 1 electronic levels (ΔE S 2 S 1 ) of the two main types of impurity centers formed by molecules of a given porphyrin in the crystal matrix are found to significantly differ from each other, the values of this difference (δΔE S 2 S 1 ) being considerably greater for tetramethyldibenzoporphin, δΔE S 2 S 1 =228cm -1 , than for the two other porphyrins. At the same time, the energies of the unperturbed vibrational states of the S 1 electronic level participating in the resonance are very close to each other for these two sites

  11. The effect of strong intermolecular and chemical interactions on the compatibility of polymers

    International Nuclear Information System (INIS)

    Askadskii, Andrei A

    1999-01-01

    The data on compatibility and on the properties of polymer blends are generalised. The emphasis is placed on the formation of strong intermolecular interactions (dipole-dipole interaction and hydrogen bonding) between the components of blends, as well as on the chemical reactions between them. A criterion for the prediction of compatibility of polymers is described in detail. Different cases of compatibility are considered and the dependences of the glass transition temperatures on the composition of blends are analysed. The published data on the effect of strong intermolecular interactions between the blend components on the glass transition temperature are considered. The preparation of interpolymers is described whose macromolecules are composed of incompatible polymers, which leads to the so-called 'forced compatibility.' The bibliography includes 80 references.

  12. 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

    to the axis perpendicular to the phenylacetylene plane and containing the center of mass. The calculated interaction energy is -418.9 cm(-1). To check further the potential, we obtain the rovibrational spectrum of the complex and the results are compared to the available experimental data. (C) 2012 American......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...... extended with a series of 3s3p2d1flg midbond functions. The potential is characterized by two equivalent global minima where the Ar atom is located above and below the phenylacetylene plane at a distance of 3.5781 angstrom from the molecular center of mass and at an angle of 9.08 degrees with respect...

  13. Pharmaceutical cocrystals, salts and multicomponent systems; intermolecular interactions and property based design.

    Science.gov (United States)

    Berry, David J; Steed, Jonathan W

    2017-08-01

    As small molecule drugs become harder to develop and less cost effective for patient use, efficient strategies for their property improvement become increasingly important to global health initiatives. Improvements in the physical properties of Active Pharmaceutical Ingredients (APIs), without changes in the covalent chemistry, have long been possible through the application of binary component solids. This was first achieved through the use of pharmaceutical salts, within the last 10-15years with cocrystals and more recently coamorphous systems have also been consciously applied to this problem. In order to rationally discover the best multicomponent phase for drug development, intermolecular interactions need to be considered at all stages of the process. This review highlights the current thinking in this area and the state of the art in: pharmaceutical multicomponent phase design, the intermolecular interactions in these phases, the implications of these interactions on the material properties and the pharmacokinetics in a patient. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Study of intermolecular interactions in binary mixtures of ethanol in methanol

    Science.gov (United States)

    Maharolkar, Aruna P.; Khirade, P. W.; Murugkar, A. G.

    2016-05-01

    Present paper deals with study of physicochemical properties like viscosity, density and refractive index for the binary mixtures of ethanol and methanol over the entire concentration range were measured at 298.15 K. The experimental data further used to determine the excess properties viz. excess molar volume, excess viscosity, excess molar refraction. The values of excess properties further fitted with Redlich-Kister (R-K Fit) equation to calculate the binary coefficients and standard deviation. The resulting excess parameters are used to indicate the presence of intermolecular interactions and strength of intermolecular interactions between the molecules in the binary mixtures. Excess parameters indicate structure making factor in the mixture predominates in the system.

  15. 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.

  16. INTERACTIONS: DESIGN, IMPLEMENTATION AND EVALUATION OF A COMPUTATIONAL TOOL FOR TEACHING INTERMOLECULAR FORCES IN HIGHER EDUCATION

    Directory of Open Access Journals (Sweden)

    Francisco Geraldo Barbosa

    2015-12-01

    Full Text Available Intermolecular forces are a useful concept that can explain the attraction between particulate matter as well as numerous phenomena in our lives such as viscosity, solubility, drug interactions, and dyeing of fibers. However, studies show that students have difficulty understanding this important concept, which has led us to develop a free educational software in English and Portuguese. The software can be used interactively by teachers and students, thus facilitating better understanding. Professors and students, both graduate and undergraduate, were questioned about the software quality and its intuitiveness of use, facility of navigation, and pedagogical application using a Likert scale. The results led to the conclusion that the developed computer application can be characterized as an auxiliary tool to assist teachers in their lectures and students in their learning process of intermolecular forces.

  17. Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

    Energy Technology Data Exchange (ETDEWEB)

    Hestand, Nicholas J.; Spano, Frank C. [Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122 (United States)

    2015-12-28

    The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (t{sub e}) and hole (t{sub h}) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product t{sub e}t{sub h} and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in “null-aggregates” which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.

  18. Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

    International Nuclear Information System (INIS)

    Hestand, Nicholas J.; Spano, Frank C.

    2015-01-01

    The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (t e ) and hole (t h ) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product t e t h and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in “null-aggregates” which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems

  19. 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

  20. Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

    Science.gov (United States)

    Beauchamp, Guy

    2008-10-23

    This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

  1. An optimized intermolecular force field for hydrogen-bonded organic molecular crystals using atomic multipole electrostatics

    International Nuclear Information System (INIS)

    Pyzer-Knapp, Edward O.; Thompson, Hugh P. G.; Day, Graeme M.

    2016-01-01

    An empirically parameterized intermolecular force field is developed for crystal structure modelling and prediction. The model is optimized for use with an atomic multipole description of electrostatic interactions. We present a re-parameterization of a popular intermolecular force field for describing intermolecular interactions in the organic solid state. Specifically we optimize the performance of the exp-6 force field when used in conjunction with atomic multipole electrostatics. We also parameterize force fields that are optimized for use with multipoles derived from polarized molecular electron densities, to account for induction effects in molecular crystals. Parameterization is performed against a set of 186 experimentally determined, low-temperature crystal structures and 53 measured sublimation enthalpies of hydrogen-bonding organic molecules. The resulting force fields are tested on a validation set of 129 crystal structures and show improved reproduction of the structures and lattice energies of a range of organic molecular crystals compared with the original force field with atomic partial charge electrostatics. Unit-cell dimensions of the validation set are typically reproduced to within 3% with the re-parameterized force fields. Lattice energies, which were all included during parameterization, are systematically underestimated when compared with measured sublimation enthalpies, with mean absolute errors of between 7.4 and 9.0%

  2. Theoretical Analysis of Proton Relays in Electrochemical Proton-Coupled Electron Transfer

    International Nuclear Information System (INIS)

    Auer, Benjamin; Fernandez, Laura; Hammes-Schiffer, Sharon

    2011-01-01

    The coupling of long-range electron transfer to proton transport over multiple sites plays a vital role in many biological and chemical processes. Recently a molecule with a hydrogen-bond relay inserted between the proton donor and acceptor sites in a proton-coupled electron transfer (PCET) system was studied electrochemically. The standard rate constants and kinetic isotope effects (KIEs) were measured experimentally for this system and a related single proton transfer system. In the present paper, these systems are studied theoretically using vibronically nonadiabatic rate constant expressions for electrochemical PCET. Application of this approach to proton relays requires the calculation of multidimensional proton vibrational wavefunctions and incorporation of multiple proton donor-acceptor motions. The calculated KIEs and relative standard rate constants for the single and double proton transfer systems are in agreement with the experimental data. The calculations indicate that the standard rate constant is lower for the double proton transfer system because of the smaller overlap integral between the ground state reduced and oxidized proton vibrational wavefunctions for this system, resulting in greater contributions from excited electron-proton vibronic states with higher free energy barriers. The decrease in proton donor-acceptor distances due to thermal fluctuations and the contributions from excited electron-proton vibronic states play important roles in proton relay systems. The theory suggests that the PCET rate constant may be increased by decreasing the equilibrium proton donor-acceptor distances or modifying the thermal motions of the molecule to facilitate the concurrent decrease of these distances. The submission of this journal article in ERIA is a requirement of the EFRC subcontract with Pennsylvania State University collaborators to get publications to OSTI.

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

    KAUST Repository

    Sutton, Christopher; Marshall, Michael S.; Sherrill, C. David; Risko, Chad; Bredas, Jean-Luc

    2015-01-01

    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

  4. 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.

  5. Noncovalent Intermolecular Interactions in Organic Electronic Materials: Implications for the Molecular Packing vs Electronic Properties of Acenes

    KAUST Repository

    Sutton, Christopher; Risko, Chad; Bredas, Jean-Luc

    2015-01-01

    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

  6. Morse-Morse-Spline-Van der Waals intermolecular potential suitable for hexafluoride gases

    International Nuclear Information System (INIS)

    Coroiu, Ilioara

    2004-01-01

    Several effective isotopic pair potential functions have been proposed to characterize the bulk properties of quasispherical molecules, in particular the hexafluorides, but none got a success. Unfortunately, these potentials have repulsive walls steeper than those which describe the hexafluorides. That these intermolecular potentials are not quite adequate is shown by the lack of complete agreement between theory and experiment even for the rare gases. Not long ago, R. A. Aziz et al. have constructed a Morse-Morse-Spline-Van der Waals (MMSV) potential. The MMSV potential incorporates the determination of C 6 dispersion coefficient and it reasonably correlates second virial coefficients and viscosity data of sulphur hexafluoride at the same time. None of the potential functions previously proposed in literature could predict these properties simultaneously. We calculated the second virial coefficients and a large number of Chapman-Cowling collision integrals for this improved intermolecular potential, the MMSV potential. The results were tabulated for a large reduced temperature range, kT/ε from 0.1 to 100. The treatment was entirely classical and no corrections for quantum effects were made. The higher approximations to the transport coefficients and the isotopic thermal diffusion factor were also calculated and tabulated for the same range. In this paper we present the evaluation of the uranium hexafluoride potential parameters for the MMSV intermolecular potential. To find a single set of potential parameters which could predict all the transport properties (viscosity, thermal conductivity, self diffusion, etc.), as well as the second virial coefficients, simultaneously, the method suggested by Morizot and a large assortment of literature data were used. Our results emphasized that the Morse-Morse-Spline-Van der Waals potential have the best overall predictive ability for gaseous hexafluoride data, certain for uranium hexafluoride. (author)

  7. Intermolecular interactions between σ- and π-holes of bromopentafluorobenzene and pyridine: computational and experimental investigations.

    Science.gov (United States)

    Yang, Fang-Ling; Yang, Xing; Wu, Rui-Zhi; Yan, Chao-Xian; Yang, Fan; Ye, Weichun; Zhang, Liang-Wei; Zhou, Pan-Pan

    2018-04-25

    The characters of σ- and π-holes of bromopentafluorobenzene (C6F5Br) enable it to interact with an electron-rich atom or group like pyridine which possesses an electron lone-pair N atom and a π ring. Theoretical studies of intermolecular interactions between C6F5Br and C5H5N have been carried out at the M06-2X/aug-cc-pVDZ level without and with the counterpoise method, together with single point calculations at M06-2X/TZVP, wB97-XD/aug-cc-pVDZ and CCSD(T)/aug-cc-pVDZ levels. The σ- and π-holes of C6F5Br exhibiting positive electrostatic potentials make these sites favorably interact with the N atom and the π ring of C5H5N with negative electrostatic potentials, leading to five different dimers connected by a σ-holen bond, a σ-holeπ bond or a π-holeπ bond. Their geometrical structures, characteristics, nature and spectroscopy behaviors were systematically investigated. EDA analyses reveal that the driving forces in these dimers are different. NCI, QTAIM and NBO analyses confirm the existence of intermolecular interactions formed via σ- and π-holes of C6F5Br and the N atom and the π ring of C5H5N. The experimental IR and Raman spectra gave us important information about the formation of molecular complexes between C6F5Br and C5H5N. We expect that the results could provide valuable insights into the investigation of intermolecular interactions involving σ- and π-holes.

  8. 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.

  9. 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...

  10. Intermolecular Interactions between Eosin Y and Caffeine Using 1H-NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Macduff O. Okuom

    2013-01-01

    Full Text Available DETECHIP has been used in testing analytes including caffeine, cocaine, and tetrahydrocannabinol (THC from marijuana, as well as date rape and club drugs such as flunitrazepam, gamma-hydroxybutyric acid (GHB, and methamphetamine. This study investigates the intermolecular interaction between DETECHIP sensor eosin Y (DC1 and the analyte (caffeine that is responsible for the fluorescence and color changes observed in the actual array. Using 1H-NMR, 1H-COSY, and 1H-DOSY NMR methods, a proton exchange from C-8 of caffeine to eosin Y is proposed.

  11. Combined experimental and theoretical study of the mechanism and enantioselectivity of palladium-catalyzed intermolecular Heck coupling

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Norrby, Per-Ola; Kaukoranta, Päivi

    2008-01-01

    . The steric interactions in this transition state fully account for the enantioselectivity observed with the ligands studied. The calculations also predict relative reactivity and nonlinear mixing effects for the investigated ligands; these predictions are fully validated by experimental testing. Finally......The asymmetric Heck reaction using P,N-ligands has been studied by a combination of theoretical and experimental methods. The reaction follows Halpern-style selectivity; that is, the major isomer is produced from the least favored form of the pre-insertion intermediate. The initially formed Ph......, the low conversion observed with some catalysts was found to be caused by inactivation due to weak binding of the ligand to Pd(0). Adding monodentate PPh3 alleviated the precipitation problem without deteriorating the enantioselectivity and led to one of the most effective catalytic systems to date....

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

    Energy Technology Data Exchange (ETDEWEB)

    Makarewicz, Jan, E-mail: jama@amu.edu.pl; Shirkov, Leonid [Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań (Poland)

    2016-05-28

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

  13. Intermolecular Modes between LH2 Bacteriochlorophylls and Protein Residues: The Effect on the Excitation Energies.

    Science.gov (United States)

    Anda, André; De Vico, Luca; Hansen, Thorsten

    2017-06-08

    Light-harvesting system 2 (LH2) executes the primary processes of photosynthesis in purple bacteria; photon absorption, and energy transportation to the reaction center. A detailed mechanistic insight into these operations is obscured by the complexity of the light-harvesting systems, particularly by the chromophore-environment interaction. In this work, we focus on the effects of the protein residues that are ligated to the bacteriochlorophylls (BChls) and construct potential energy surfaces of the ground and first optically excited state for the various BChl-residue systems where we in each case consider two degrees of freedom in the intermolecular region. We find that the excitation energies are only slightly affected by the considered modes. In addition, we see that axial ligands and hydrogen-bonded residues have opposite effects on both excitation energies and oscillator strengths by comparing to the isolated BChls. Our results indicate that only a small part of the chromophore-environment interaction can be associated with the intermolecular region between a BChl and an adjacent residue, but that it may be possible to selectively raise or lower the excitation energy at the axial and planar residue positions, respectively.

  14. Intermolecular cope-type hydroamination of alkenes and alkynes using hydroxylamines.

    Science.gov (United States)

    Moran, Joseph; Gorelsky, Serge I; Dimitrijevic, Elena; Lebrun, Marie-Eve; Bédard, Anne-Catherine; Séguin, Catherine; Beauchemin, André M

    2008-12-31

    The development of the Cope-type hydroamination as a method for the metal- and acid-free intermolecular hydroamination of hydroxylamines with alkenes and alkynes is described. Aqueous hydroxylamine reacts efficiently with alkynes in a Markovnikov fashion to give oximes and with strained alkenes to give N-alkylhydroxylamines, while unstrained alkenes are more challenging. N-Alkylhydroxylamines also display similar reactivity with strained alkenes and give modest to good yields with vinylarenes. Electron-rich vinylarenes lead to branched products while electron-deficient vinylarenes give linear products. A beneficial additive effect is observed with sodium cyanoborohydride, the extent of which is dependent on the structure of the hydroxylamine. The reaction conditions are found to be compatible with common protecting groups, free OH and NH bonds, as well as bromoarenes. Both experimental and theoretical results suggest the proton transfer step of the N-oxide intermediate is of vital importance in the intermolecular reactions of alkenes. Details are disclosed concerning optimization, reaction scope, limitations, and theoretical analysis by DFT, which includes a detailed molecular orbital description for the concerted hydroamination process and an exhaustive set of calculated potential energy surfaces for the reactions of various alkenes, alkynes, and hydroxylamines.

  15. Effect of intermolecular hydrogen bonding, vibrational analysis and molecular structure of 4-chlorobenzothioamide

    Science.gov (United States)

    Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

    2013-09-01

    In the present work, the experimental and theoretical vibrational spectra of 4-chlorobenzothioamide were investigated. The FT-IR (400-4000 cm-1) and μ-Raman spectra (100-4000 cm-1) of 4-chlorobenzothioamide in the solid phase were recorded. The geometric parameters (bond lengths and bond angles), vibrational frequencies, Infrared and Raman intensities of the title molecule in the ground state were calculated using ab initio Hartree-Fock and density functional theory (B3LYP) methods with the 6-311++G(d,p) basis set for the first time. The optimized geometric parameters and the theoretical vibrational frequencies were found to be in good agreement with the corresponding experimental data and with the results found in the literature. The vibrational frequencies were assigned based on the potential energy distribution using the VEDA 4 program. The dimeric form of 4-chlorobenzothioamide was also simulated to evaluate the effect of intermolecular hydrogen bonding on the vibrational frequencies. It was observed that the Nsbnd H stretching modes shifted to lower frequencies, while the in-plane and out-of-plane bending modes shifted to higher frequencies due to the intermolecular Nsbnd H⋯S hydrogen bond. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and diagrams were presented.

  16. Effect of intermolecular hydrogen bonding, vibrational analysis and molecular structure of a biomolecule: 5-Hydroxymethyluracil

    Science.gov (United States)

    Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

    2014-06-01

    In the present work, the experimental and theoretical vibrational spectra of 5-hydroxymethyluracil were investigated. The FT-IR (4000-400 cm-1) spectrum of the molecule in the solid phase was recorded. The geometric parameters (bond lengths and bond angles), vibrational frequencies, Infrared intensities of the title molecule in the ground state were calculated using density functional B3LYP and M06-2X methods with the 6-311++G(d,p) basis set for the first time. The optimized geometric parameters and theoretical vibrational frequencies were found to be in good agreement with the corresponding experimental data, and with the results found in the literature. The vibrational frequencies were assigned based on the potential energy distribution using the VEDA 4 program. The dimeric form of 5-hydroxymethyluracil molecule was also simulated to evaluate the effect of intermolecular hydrogen bonding on its vibrational frequencies. It was observed that the Nsbnd H stretching modes shifted to lower frequencies, while its in-plane and out-of-plane bending modes shifted to higher frequencies due to the intermolecular Nsbnd H⋯O hydrogen bond. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and diagrams were presented.

  17. Quantitative assessment of intermolecular interactions by atomic force microscopy imaging using copper oxide tips

    Science.gov (United States)

    Mönig, Harry; Amirjalayer, Saeed; Timmer, Alexander; Hu, Zhixin; Liu, Lacheng; Díaz Arado, Oscar; Cnudde, Marvin; Strassert, Cristian Alejandro; Ji, Wei; Rohlfing, Michael; Fuchs, Harald

    2018-05-01

    Atomic force microscopy is an impressive tool with which to directly resolve the bonding structure of organic compounds1-5. The methodology usually involves chemical passivation of the probe-tip termination by attaching single molecules or atoms such as CO or Xe (refs 1,6-9). However, these probe particles are only weakly connected to the metallic apex, which results in considerable dynamic deflection. This probe particle deflection leads to pronounced image distortions, systematic overestimation of bond lengths, and in some cases even spurious bond-like contrast features, thus inhibiting reliable data interpretation8-12. Recently, an alternative approach to tip passivation has been used in which slightly indenting a tip into oxidized copper substrates and subsequent contrast analysis allows for the verification of an oxygen-terminated Cu tip13-15. Here we show that, due to the covalently bound configuration of the terminal oxygen atom, this copper oxide tip (CuOx tip) has a high structural stability, allowing not only a quantitative determination of individual bond lengths and access to bond order effects, but also reliable intermolecular bond characterization. In particular, by removing the previous limitations of flexible probe particles, we are able to provide conclusive experimental evidence for an unusual intermolecular N-Au-N three-centre bond. Furthermore, we demonstrate that CuOx tips allow the characterization of the strength and configuration of individual hydrogen bonds within a molecular assembly.

  18. 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.

  19. Thz Spectroscopy and DFT Modeling of Intermolecular Vibrations in Hydrophobic Amino Acids

    Science.gov (United States)

    Williams, michael R. C.; Aschaffenburg, Daniel J.; Schmuttenmaer, Charles A.

    2013-06-01

    Vibrations that involve intermolecular displacements occur in molecular crystals at frequencies in the 0.5-5 THz range (˜15-165 cm^{-1}), and these motions are direct indicators of the interaction potential between the molecules. The intermolecular potential energy surface of crystalline hydrophobic amino acids is inherently interesting simply because of the wide variety of forces (electrostatic, dipole-dipole, hydrogen-bonding, van der Waals) that are present. Furthermore, an understanding of these particular interactions is immediately relevant to important topics like protein conformation and pharmaceutical polymorphism. We measured the low-frequency absorption spectra of several polycrystalline hydrophobic amino acids using THz time-domain spectroscopy, and in addition we carried out DFT calculations using periodic boundary conditions and an exchange-correlation functional that accounts for van der Waals dispersion forces. We chose to investigate a series of similar amino acids with closely analogous unit cells (leucine, isoleucine, and allo-isoleucine, in racemic or pseudo-racemic mixtures). This allows us to consider trends in the vibrational spectra as a function of small changes in molecular arrangement and/or crystal geometry. In this way, we gain confidence that peak assignments are not based on serendipitous similarities between calculated and observed features.

  20. Photophysical and computational investigation of the intermolecular interactions of pyrene with phenothiazine and promazine

    Energy Technology Data Exchange (ETDEWEB)

    Güloğlu, Pınar; Acar, Nursel, E-mail: nursel.acar@ege.edu.tr

    2016-10-20

    Highlights: • Intermolecular interactions of pyrene with phenothiazine/promazine were investigated. • All investigated systems were optimized at ωB97XD/6-31G(d,p) level in gas phase. • The electronic transitions were determined using frontier orbitals. • Both Py–Pheno and Py–Prom are potential candidates for charge transfer systems. - Abstract: The intermolecular interactions between the pyrene (Py) (as acceptor) and phenothiazine (Pheno), promazine (Prom) (as donors) were investigated using UV/Vis absorption and fluorescence spectroscopy. Fluorescence quenching rate constants for Py–Pheno and Py–Prom systems have been calculated approximately 10{sup 10} M{sup −1} s{sup −1}, indicating diffusion controlled processes. A computational investigation has also been carried out in gas phase at ωB97XD/6-31G(d,p) level. Time-dependent density functional theory (TDDFT) was used to calculate the electronic transitions of molecules at B3LYP/6-311++G(d,p) level. Total electronic energies, complexation energies, free energy differences, excitation wavelengths, and HOMO–LUMO energy gaps are discussed in gas phase. Analyses of first excited singlet states have indicated charge transfers transitions between Py and Pheno, Prom through π–π stacking in gas phase at 433 nm and 466 nm, respectively. Due to its charge transfer character, Py–Pheno and Py–Prom systems seem to be appropriate models to investigate and design photosensitive materials.

  1. 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.

  2. 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.

  3. Effects of pair correlation functions on intermolecular nuclear relaxation by translational and rotational diffusion in liquids

    International Nuclear Information System (INIS)

    Fries, P.

    1978-01-01

    In order to study the intermolecular relaxation due to magnetic dipolar interactions, we calculate the spectral densities resulting from random translational and rotational motions of spherical molecules carrying off-centre spins. The relative translational motion is treated in the frame-work of a general diffusion equation (the Smoluchowski equation) which takes into account the existence of effective forces between the molecules. This model implies a pair correlation function. i.e. a non unifom relative distribution of the molecules. The analytical calculations are carried out by taking correctly into account the hard sphere boundary conditions for the molecules. Explicit numerical calculations of the spectral densities are performed using finite difference methods and the pair correlation function of Verlet and Weiss obtained by computer experiments. The resulting calculations allow one to interpret the relaxation exhibited by benzene and some of its monohalogen derivatives which has been measured by Jonas et al. at various pressures. The effects of pair correlation and eccentricity contribute to a noticeable enhancement of the spectral densities, especially as the frequency increases. The translational correlation times calculated from the Stokes formula and those deduced from intermolecular relaxation studies are compared. It is shown that in order to distinguish which of the dynamical models is appropriate, measurements must be made as a function of frequency [fr

  4. Predicting Keto-Enol Equilibrium from Combining UV/Visible Absorption Spectroscopy with Quantum Chemical Calculations of Vibronic Structures for Many Excited States. A Case Study on Salicylideneanilines.

    Science.gov (United States)

    Zutterman, Freddy; Louant, Orian; Mercier, Gabriel; Leyssens, Tom; Champagne, Benoît

    2018-06-21

    Salicylideneanilines are characterized by a tautomer equilibrium, between an enol and a keto form of different colors, at the origin of their remarkable thermochromic, solvatochromic, and photochromic properties. The enol form is usually the most stable but appropriate choice of substituents and conditions (solvent, crystal, host compound) can displace the equilibrium toward the keto form so that there is a need for fast prediction of the keto:enol abundance ratio. Here we demonstrate the reliability of a combined theoretical-experimental method, based on comparing simulated and measured UV/visible absorption spectra, to determine this keto/enol ratio. The calculations of the excitation energies, oscillator strengths, and vibronic structures of both enol and keto forms are performed for all excited states absorbing in the relevant (visible and near-UV) wavelength range at the time-dependent density functional theory level by accounting for solvent effects using the polarizable continuum model. This approach is illustrated for two salicylideneaniline derivatives, which are present, in solution, under the form of keto-enol mixtures. The results are compared to those of chemometric analysis as well as ab initio predictions of the reaction free enthalpies.

  5. Intermolecular potential and rovibrational states of the H{sub 2}O-D{sub 2} complex

    Energy Technology Data Exchange (ETDEWEB)

    Avoird, Ad van der, E-mail: A.vanderAvoird@theochem.ru.nl [Theoretical Chemistry, Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands); Scribano, Yohann [Laboratoire Interdisciplinaire Carnot de Bourgogne-UMR 5209, CNRS-Universite de Bourgogne, 9 Av. Alain Savary, B.P. 47870, F-21078 Dijon Cedex (France); Faure, Alexandre [UJF-Grenoble 1/CNRS, Institut de Planetologie et d' Astrophysique de Grenoble (IPAG) UMR 5274, Grenoble F-38041 (France); Weida, Miles J. [Daylight Solutions, 15378 Avenue of Science, San Diego, CA 92128 (United States); Fair, Joanna R. [Department of Radiology, MSC10 5530, 1 University of New Mexico, Albuquerque, NM 87131-0001 (United States); Nesbitt, David J. [JILA, University of Colorado and National Institute of Standards and Technology, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309-0440 (United States)

    2012-05-03

    Graphical abstract: H{sub 2}O-D{sub 2} potential surface and pH{sub 2}O-oD{sub 2} ground state wave function, for planar geometries. Highlights: Black-Right-Pointing-Pointer The interaction between H{sub 2}O and H{sub 2} is of great astrophysical interest. Black-Right-Pointing-Pointer The rovibrational states of H{sub 2}O-D{sub 2} were computed on an ab initio potential surface. Black-Right-Pointing-Pointer Results are compared with the rovibrational states of H{sub 2}O-H{sub 2} computed recently. Black-Right-Pointing-Pointer We measured the high-resolution infrared spectrum of H{sub 2}O-D{sub 2} in the H{sub 2}O bend region. Black-Right-Pointing-Pointer Comparison with the calculations provides information on H{sub 2}O-H{sub 2} potential surface. - Abstract: A five-dimensional intermolecular potential for H{sub 2}O-D{sub 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. Kedzuch, J. Noga, J. Chem. Phys. 129 (2008) 134306] by averaging over the ground state vibrational wave functions of H{sub 2}O and D{sub 2}. On this five-dimensional potential with a well depth D{sub e} of 232.12 cm{sup -1} we calculated the bound rovibrational levels of H{sub 2}O-D{sub 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{sub 2}O and D{sub 2}, as well as to inversion symmetry. As expected, the H{sub 2}O-D{sub 2} dimer is more strongly bound than its H{sub 2}O-H{sub 2} isotopologue [cf. A. van der Avoird, D.J. Nesbitt, J. Chem. Phys. 134 (2011) 044314], with dissociation energies D

  6. 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

  7. Similarities between intra- and intermolecular hydrogen bonds in RNA kissing complexes found by means of cross-correlated relaxation

    International Nuclear Information System (INIS)

    Dittmer, Jens; Kim, Chul-Hyun; Bodenhausen, Geoffrey

    2003-01-01

    The bond lengths and dynamics of intra- and intermolecular hydrogen bonds in an RNA kissing complex have been characterized by determining the NMR relaxation rates of various double- and triple-quantum coherences that involve an imino proton and two neighboring nitrogen-15 nuclei belonging to opposite bases. New experiments allow one to determine the chemical shift anisotropy of the imino protons. The bond lengths derived from dipolar relaxation and the lack of modulations of the nitrogen chemical shifts indicate that the intermolecular hydrogen bonds which hold the kissing complex together are very similar to the intramolecular hydrogen bonds in the double-stranded stem of the RNA

  8. Vibronic effects and destruction of exciton coherence in optical spectra of J-aggregates: A variational polaron transformation approach

    Energy Technology Data Exchange (ETDEWEB)

    Bloemsma, E.A.; Silvis, M.H.; Stradomska, A.; Knoester, J., E-mail: j.knoester@rug.nl

    2016-12-20

    Using a symmetry adapted polaron transformation of the Holstein Hamiltonian, we study the interplay of electronic excitation-vibration couplings, resonance excitation transfer interactions, and temperature in the linear absorption spectra of molecular J-aggregates. Semi-analytical expressions for the spectra are derived and compared with results obtained from direct numerical diagonalization of the Hamiltonian in the two-particle basis set representation. At zero temperature, we show that our polaron transformation reproduces both the collective (exciton) and single-molecule (vibrational) optical response associated with the appropriate standard perturbation limits. Specifically, for the molecular dimer excellent agreement with the spectra from the two-particle approach for the entire range of model parameters is obtained. This is in marked contrast to commonly used polaron transformations. Upon increasing the temperature, the spectra show a transition from the collective to the individual molecular features, which results from the thermal destruction of the exciton coherence.

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

    International Nuclear Information System (INIS)

    Heßelmann, Andreas; Korona, Tatiana

    2014-01-01

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

  10. Graphene-enhanced intermolecular interaction at interface between copper- and cobalt-phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Dou, Wei-Dong [Department of Physics, Shaoxing University, Shaoxing 312000 (China); Center of Super-Diamond and Advanced Films (COSDAF) and Department of Physics and Material Science, City University of Hong Kong, Hong Kong (China); Huang, Shu-Ping [Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069 (United States); Lee, Chun-Sing, E-mail: apcslee@cityu.edu.hk [Center of Super-Diamond and Advanced Films (COSDAF) and Department of Physics and Material Science, City University of Hong Kong, Hong Kong (China)

    2015-10-07

    Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π–π interaction between CoPc and CuPc. Analysis based on X-ray photoelectron spectroscopy and density functional theory reveals that the decrease in the work function for the CuPc/CoPc/graphene system is induced by the intermolecular interaction between CuPc and CoPc which is enhanced owning to the peculiar electronic properties at the CoPc-graphene interface.

  11. 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...

  12. Influence of pressure on the crystallization of systems characterized by different intermolecular attraction

    Science.gov (United States)

    Koperwas, K.; Affouard, F.; Gerges, J.; Valdes, L.-C.; Adrjanowicz, K.; Paluch, M.

    2017-12-01

    In this paper, we examine, in terms of the classical nucleation theory, how the strengthening of the attractive intermolecular interactions influences the crystallization process for systems like Lennard-Jones at different isobaric conditions. For this purpose, we modify the standard Lennard-Jones potential, and as a result, we obtain three different systems characterized by various strengths of attractive potentials occurring between molecules, which are in direct relationship to the physical quantities describing molecules, e.g., its polarizability or dipole moment. Based on performed analysis, we demonstrate that the molecular attraction primarily impacts the thermodynamics of the interface between liquid and crystal. This is reflected in the behavior of nucleation and overall crystallization rates during compression of the system.

  13. 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)

  14. Intermolecular Force Field Parameters Optimization for Computer Simulations of CH4 in ZIF-8

    Directory of Open Access Journals (Sweden)

    Phannika Kanthima

    2016-01-01

    Full Text Available The differential evolution (DE algorithm is applied for obtaining the optimized intermolecular interaction parameters between CH4 and 2-methylimidazolate ([C4N2H5]− using quantum binding energies of CH4-[C4N2H5]− complexes. The initial parameters and their upper/lower bounds are obtained from the general AMBER force field. The DE optimized and the AMBER parameters are then used in the molecular dynamics (MD simulations of CH4 molecules in the frameworks of ZIF-8. The results show that the DE parameters are better for representing the quantum interaction energies than the AMBER parameters. The dynamical and structural behaviors obtained from MD simulations with both sets of parameters are also of notable differences.

  15. 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.

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

    International Nuclear Information System (INIS)

    Karayel, A.; Özbey, S.; Ayhan-Kılcıgil, G.; Kuş, C.

    2015-01-01

    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

  17. 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 ...

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

    Science.gov (United States)

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

    2015-06-28

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

  19. Dielectric behaviour and intermolecular association between L(+) ascorbic acid and ethanol

    International Nuclear Information System (INIS)

    Rudyk, R.A.; Torres, M.C.; Acuna Molina, M.A.

    1990-01-01

    In order to determine the dipole moment of L(+) ascorbic acid and the relation to its structure the experimental variations of permitivities, refractive indices and specific volumes of a series of dilute ethanolic solutions at 25 deg C were examined. The average moment (μ) using Buckingham equation was found to be 5,58 D considering the spherical approximation and 7,81 D if the ellipsoidal form factor was considered. The calculated μ value through vectorial addition was 4,98 D. The solute partial molal volume in the studied range was calculated to be 94,73 cm 3 instead of the theoretical value of 106,71 cm 3 . Both discrepancies are attributed to intermolecular solute-solvent interactions. A possible electronic displacement which favours hydrogen bonding with the solvent is postulated. (Author) [es

  20. Importance of the Donor:Fullerene intermolecular arrangement for high-efficiency organic photovoltaics

    KAUST Repository

    Graham, Kenneth; Cabanetos, Clement; Jahnke, Justin P.; Idso, Matthew N.; El Labban, Abdulrahman; Ngongang Ndjawa, Guy Olivier; Heumueller, Thomas; Vandewal, Koen; Salleo, Alberto; Chmelka, Bradley F.; Amassian, Aram; Beaujuge, Pierre; McGehee, Michael D.

    2014-01-01

    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. 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

  2. Rewetting phenomena and their relation to intermolecular forces between a hot wall and the fluid

    International Nuclear Information System (INIS)

    Gerweck, V.

    1989-12-01

    The rewetting phenomena and the different physical concepts which are used in their modelisation are reviewed. The present work studies the effect of the intermolecular forces between the hot wall and the fluid on this phase transition. Using suitable approximations, a local equation of state is obtained by the treatment of the fluid-fluid and fluid-wall intermolecular interactions. This local equation of state depends on the distance from the wall, and the critical pressure and temperature become a function of the distance from the wall, whereas the critical density is left constant throughout the fluid. At the wall, the critical pressure and temperature are half their bulk values and increase towards the bulk value as the distance from the wall increases. The penetration of a temperature profile in this fluid is studied by assuming that the liquid density is not strongly affected by this temperature profile as long as there is no phase transition. It is shown that the phase transition will occur extremely rapidly when the interfacial temperature upon contact is higher than the minimum of the local spinodal temperature, which varies with the distance from the wall. The result ist cast in the form of an interfacial rewetting temperature fT c above which rewetting of the surface by liquid-wall contacts is not expected because these contacts will be terminated in extremely short times. Comparing the theory with available data shows that in the usual rewetting situations the theory reduces to the use of the bulk spinodal temperature. For surfaces coated with poorly wetted materials the correction factor due to surface effects applies, reducing the rewetting temperature, in agreement with the experimental data. For liquid metals it appears that the theory is applied in a region where the basic theoretical approximations are very coarse; but even in that case the experimental trend is qualitatively predicted by the theory. (author) 43 figs., 11 tabs., 105 refs

  3. 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.

  4. Enhanced Electron-Phonon Coupling at Metal Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Plummer, Ward E.

    2010-08-04

    The Born-Oppenheimer approximation (BOA) decouples electronic from nuclear motion, providing a focal point for most quantum mechanics textbooks. However, a multitude of important chemical, physical and biological phenomena are driven by violations of this approximation. Vibronic interactions are a necessary ingredient in any process that makes or breaks a covalent bond, for example, conventional catalysis or enzymatically delivered biological reactions. Metastable phenomena associated with defects and dopants in semiconductors, oxides, and glasses entail violation of the BOA. Charge exchange in inorganic polymers, organic slats and biological systems involves charge- induced distortions of the local structure. A classic example is conventional superconductivity, which is driven by the electron-lattice interaction. High-resolution angle-resolved photoemission experiments are yielding new insight into the microscopic origin of electron-phonon coupling (EPC) in anisotropic two-dimensional systems. Our recent surface phonon measurement on the surface of a high-Tc material clearly indicates an important momentum dependent EPC in these materials. In the last few years we have shifted our research focus from solely looking at electron phonon coupling to examining the structure/functionality relationship at the surface of complex transition metal compounds. The investigation on electron phonon coupling has allowed us to move to systems where there is coupling between the lattice, the electrons and the spin.

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

    DEFF Research Database (Denmark)

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

    1985-01-01

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

  6. 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...

  7. Coiodação de alquenos com nucleófilos oxigenados: reações intermoleculares

    Directory of Open Access Journals (Sweden)

    Sanseverino Antonio Manzolillo

    2001-01-01

    Full Text Available A review on the electrophilic addition of iodine to alkenes in the presence of oxygen containing nucleophiles (cohalogenation reaction is presented. The intermolecular reactions are discussed with emphasis in methods of reaction and synthetic applications of the resulting vicinal iodo-functionalized products (iodohydrins, beta-iodoethers and beta-iodocarboxylates.

  8. Intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization reactions of 1,6-enynes with symmetrical and unsymmetrical alkynes†

    Science.gov (United States)

    Andrew Evans, P.; Sawyer, James R.; Lai, Kwong Wah; Huffman, John C.

    2006-01-01

    The crossed intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. PMID:16075089

  9. Synthesis of benzimidazoles by potassium tert-butoxide-promoted intermolecular cyclization reaction of 2-iodoanilines with nitriles.

    Science.gov (United States)

    Xiang, Shi-Kai; Tan, Wen; Zhang, Dong-Xue; Tian, Xian-Li; Feng, Chun; Wang, Bi-Qin; Zhao, Ke-Qing; Hu, Ping; Yang, Hua

    2013-11-14

    The synthesis of benzimidazoles by intermolecular cyclization reaction of 2-iodoanilines with nitriles has been developed. These reactions proceeded without the aid of any transition metals or ligands and just using KOBu(t) as the base. A variety of substituted benzimidazole derivatives can be synthesized by the approach.

  10. Effects of sodium salt types on the intermolecular interaction of sodium alginate/antarctic krill protein composite fibers.

    Science.gov (United States)

    Zhang, Rui; Guo, Jing; Liu, Yuanfa; Chen, Shuang; Zhang, Sen; Yu, Yue

    2018-06-01

    Sodium alginate (SA) and antarctic krill protein (AKP) were blended to fabricate the SA/AKP composite fibers by the conventional wet spinning method using 5% CaCl 2 as coagulation solution. The sodium salt was added to the SA/AKP solution to adjust the ionization degree and intermolecular interaction of composite system. The main purpose of this study is to investigate the influences of sodium salt types (NaCl, CH 3 COONa, Na 2 SO 4 ) on the intermolecular interaction of SA/AKP composite fibers. The intermolecular interaction, morphology, crystallinity, thermal stability and mechanical properties of SA/AKP composite fibers were analyzed by fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), x-ray diffraction (XRD), thermogravimetric analysis (TGA). The results show that the types of sodium salt have obvious influences on the content of both β-sheet, intermolecular hydrogen bond, breaking strength and surface morphology in SA/AKP composite fibers, but have a negligible effect on the crystallinity and thermal stability. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. 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

  12. A multifrequency virtual spectrometer for complex bio-organic systems: vibronic and environmental effects on the UV/Vis spectrum of chlorophyll a.

    Science.gov (United States)

    Barone, Vincenzo; Biczysko, Malgorzata; Borkowska-Panek, Monika; Bloino, Julien

    2014-10-20

    The subtle interplay of several different effects means that the interpretation and analysis of experimental spectra in terms of structural and dynamic characteristics is a challenging task. In this context, theoretical studies can be helpful, and as such, computational spectroscopy is rapidly evolving from a highly specialized research field toward a versatile and widespread tool. However, in the case of electronic spectra (e.g. UV/Vis, circular dichroism, photoelectron, and X-ray spectra), the most commonly used methods still rely on the computation of vertical excitation energies, which are further convoluted to simulate line shapes. Such treatment completely neglects the influence of nuclear motions, despite the well-recognized notion that a proper account of vibronic effects is often mandatory to correctly interpret experimental findings. Development and validation of improved models rooted into density functional theory (DFT) and its time-dependent extension (TD-DFT) is of course instrumental for the optimal balance between reliability and favorable scaling with the number of electrons. However, the implementation of easy-to-use and effective procedures to simulate vibrationally resolved electronic spectra, and their availability to a wide community of users, is at least equally important for reliable simulations of spectral line shapes for compounds of biological and technological interest. Here, such an approach has been applied to the study of the UV/Vis spectra of chlorophyll a. The results show that properly tailored approaches are feasible for state-of-the-art computational spectroscopy studies, and allow, with affordable computational resources, vibrational and environmental effects on the spectral line shapes to be taken into account for large systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Franck-Condon Simulations including Anharmonicity of the Ã(1)A''-X̃(1)A' Absorption and Single Vibronic Level Emission Spectra of HSiCl and DSiCl.

    Science.gov (United States)

    Mok, Daniel W K; Lee, Edmond P F; Chau, Foo-Tim; Dyke, John M

    2009-03-10

    RCCSD(T) and/or CASSCF/MRCI calculations have been carried out on the X̃(1)A' and Ã(1)A'' states of HSiCl employing basis sets of up to the aug-cc-pV5Z quality. Contributions from core correlation and extrapolation to the complete basis set limit were included in determining the computed equilibrium geometrical parameters and relative electronic energy of these two states of HSiCl. Franck-Condon factors which include allowance for anharmonicity and Duschinsky rotation between these two states of HSiCl and DSiCl were calculated employing RCCSD(T) and CASSCF/MRCI potential energy functions, and were used to simulate the Ã(1)A'' ← X̃(1)A' absorption and Ã(1)A'' → X̃(1)A' single vibronic level (SVL) emission spectra of HSiCl and DSiCl. Simulated absorption and experimental LIF spectra, and simulated and observed Ã(1)A''(0,0,0) → X̃(1)A' SVL emission spectra, of HSiCl and DSiCl are in very good agreement. However, agreement between simulated and observed Ã(1)A''(0,1,0) → X̃(1)A' and Ã(1)A''(0,2,1) → X̃(1)A' SVL emission spectra of DSiCl is not as good. Preliminary calculations on low-lying excited states of HSiCl suggest that vibronic interaction between low-lying vibrational levels of the Ã(1)A'' state and highly excited vibrational levels of the ã(3)A'' is possible. Such vibronic interaction may change the character of the low-lying vibrational levels of the Ã(1)A'' state, which would lead to perturbation in the SVL emission spectra from these vibrational levels.

  14. Effects of Weak Intermolecular Interactions on the Molecular Isomerism of Tricobalt Metal Chains

    International Nuclear Information System (INIS)

    Poulsen, R.; Overgaard, J.; Schulman, A.; Stergaard, C.; Murillo, C.; Spackman, M.; Iversen, B.

    2009-01-01

    Depending on the number of interstitial solvent molecules, n, crystals of the linear chain compound Co3(dipyridylamide)4Cl2·nCH2Cl2 adopt either symmetrical or unsymmetrical metal chain structures. We explore here the possible reasons for such behavior using Hirshfeld surface analysis of intermolecular interactions as well as the charge density determined from 100(1) K X-ray diffraction data on the unsymmetrical complex Co3(dipyridylamide)4Cl2·2.11CH2Cl2, u-1, and crystal structures of u-1 determined from single crystal synchrotron X-ray diffraction data at 20, 150, and 300 K. The new crystal structures are compared with previous structural results on a crystal with slightly different solvent content. This change in solvent content only affects the bond distances to atom Co(3), which are also strongly affected by temperature changes due to a spin crossover transition. Large differences in intermolecular interactions are revealed by the Hirshfeld surface analysis between symmetrical (s-1) and unsymmetrical (u-1) crystal solvates, suggesting that the molecular isomerism is strongly influenced by crystal packing effects. Topological analysis of the static electron density of u-1 suggests that there is direct metal-metal bonding for both the shorter Co(1)-Co(2) and the longer Co(2)-Co(3) contact. The approximate description of the system as a (Co2)2+-dimer and an isolated Co2+-ion is reflected in the character of the metal-ligand interactions, which are more ionic for the isolated Co(3) atom, and the topological charges Co(1)+0.50, Co(2)+0.77, and Co(3)+1.36. The two termini of u-1 are found to be very different, both in terms of structural surroundings as well as topology. The central Co(2) atom is similar to a cobalt atom in a tetragonally distorted octahedral environment resulting in preferred occupancy in the t2g orbitals. The Co(1) atom has significant deformation in the xz and yz planes (z along the chain axis, x and y toward ligands) reflecting covalent

  15. A simplified approach for the coupling of excitation energy transfer

    Energy Technology Data Exchange (ETDEWEB)

    Shi Bo [Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei 230026 (China); Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Gao Fang, E-mail: gaofang@iim.ac.cn [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); State Key Laboratory of Robotics, Shenyang Institute of Automation, Chinese Academy of Sciences, Shenyang 110016 (China); Liang Wanzhen [Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei 230026 (China); Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China)

    2012-02-06

    Highlights: Black-Right-Pointing-Pointer We propose a simple method to calculate the coupling of singlet-to-singlet and triplet-to-triplet energy transfer. Black-Right-Pointing-Pointer Coulomb term are the major contribution to the coupling of singlet-to-singlet energy transfer. Black-Right-Pointing-Pointer Effect from the intermolecular charge-transfer states dorminates in triplet-to-triplet energy transfer. Black-Right-Pointing-Pointer This method can be expanded by including correlated wavefunctions. - Abstract: A simplified approach for computing the electronic coupling of nonradiative excitation-energy transfer is proposed by following Scholes et al.'s construction on the initial and final states [G.D. Scholes, R.D. Harcourt, K.P. Ghiggino, J. Chem. Phys. 102 (1995) 9574]. The simplification is realized through defining a set of orthogonalized localized MOs, which include the polarization effect of the charge densities. The method allows calculating the coupling of both the singlet-to-singlet and triplet-to-triplet energy transfer. Numerical tests are performed for a few of dimers with different intermolecular orientations, and the results demonstrate that Coulomb term are the major contribution to the coupling of singlet-to-singlet energy transfer whereas in the case of triplet-to-triplet energy transfer, the dominant effect is arisen from the intermolecular charge-transfer states. The present application is on the Hartree-Fock level. However, the correlated wavefunctions which are normally expanded in terms of the determinant wavefunctions can be employed in the similar way.

  16. On the influence of the intermolecular potential on the wetting properties of water on silica surfaces

    Science.gov (United States)

    Pafong, E.; Geske, J.; Drossel, B.

    2016-09-01

    We study the wetting properties of water on silica surfaces using molecular dynamics (MD) simulations. To describe the intermolecular interaction between water and silica atoms, two types of interaction potential models are used: the standard BródkA and Zerda (BZ) model and the Gulmen and Thompson (GT) model. We perform an in-depth analysis of the influence of the choice of the potential on the arrangement of the water molecules in partially filled pores and on top of silica slabs. We find that at moderate pore filling ratios, the GT silica surface is completely wetted by water molecules, which agrees well with experimental findings, while the commonly used BZ surface is less hydrophilic and is only partially wetted. We interpret our simulation results using an analytical calculation of the phase diagram of water in partially filled pores. Moreover, an evaluation of the contact angle of the water droplet on top of the silica slab reveals that the interaction becomes more hydrophilic with increasing slab thickness and saturates around 2.5-3 nm, in agreement with the experimentally found value. Our analysis also shows that the hydroaffinity of the surface is mainly determined by the electrostatic interaction, but the van der Waals interaction nevertheless is strong enough that it can turn a hydrophobic surface into a hydrophilic surface.

  17. Resolution enhancement in MR spectroscopy of red bone marrow fat via intermolecular double-quantum coherences

    Science.gov (United States)

    Bao, Jianfeng; Cui, Xiaohong; Huang, Yuqing; Zhong, Jianhui; Chen, Zhong

    2015-08-01

    High-resolution 1H magnetic resonance spectroscopy (MRS) is generally inaccessible in red bone marrow (RBM) tissues using conventional MRS techniques. This is because signal from these tissues suffers from severe inhomogeneity in the main static B0 field originated from the intrinsic honeycomb structures in trabecular bone. One way to reduce effects of B0 field inhomogeneity is by using the intermolecular double quantum coherence (iDQC) technique, which has been shown in other systems to obtain signals insensitive to B0 field inhomogeneity. In the present study, we employed an iDQC approach to enhance the spectral resolution of RBM. The feasibility and performance of this method for achieving high resolution MRS was verified by experiments on phantoms and pig vertebral bone samples. Unsaturated fatty acid peaks which overlap in the conventional MRS were well resolved and identified in the iDQC spectrum. Quantitative comparison of fractions of three types of fatty acids was performed between iDQC spectra on the in situ RMB and conventional MRS on the extracted fat from the same RBM. Observations of unsaturated fatty acids with iDQC MRS may provide valuable information and may hold potential in diagnosis of diseases such as obesity, diabetes, and leukemia.

  18. 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.

  19. Determination of a silane intermolecular force field potential model from an ab initio calculation

    International Nuclear Information System (INIS)

    Li, Arvin Huang-Te; Chao, Sheng D.; Chang, Chien-Cheng

    2010-01-01

    Intermolecular interaction potentials of the silane dimer in 12 orientations have been calculated by using the Hartree-Fock (HF) self-consistent theory and the second-order Moeller-Plesset (MP2) perturbation theory. We employed basis sets from Pople's medium-size basis sets [up to 6-311++G(3df, 3pd)] and Dunning's correlation consistent basis sets (up to the triply augmented correlation-consistent polarized valence quadruple-zeta basis set). We found that the minimum energy orientations were the G and H conformers. We have suggested that the Si-H attractions, the central silicon atom size, and electronegativity play essential roles in weakly binding of a silane dimer. The calculated MP2 potential data were employed to parametrize a five-site force field for molecular simulations. The Si-Si, Si-H, and H-H interaction parameters in a pairwise-additive, site-site potential model for silane molecules were regressed from the ab initio energies.

  20. 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.

  1. Intermolecular G-quadruplex structure-based fluorescent DNA detection system.

    Science.gov (United States)

    Zhou, Hui; Wu, Zai-Sheng; Shen, Guo-Li; Yu, Ru-Qin

    2013-03-15

    Adopting multi-donors to pair with one acceptor could improve the performance of fluorogenic detection probes. However, common dyes (e.g., fluorescein) in close proximity to each other would self-quench the fluorescence, and the fluorescence is difficult to restore. In this contribution, we constructed a novel "multi-donors-to-one acceptor" fluorescent DNA detection system by means of the intermolecular G-quadruplex (IGQ) structure-based fluorescence signal enhancement combined with the hairpin oligonucleotide. The novel IGQ-hairpin system was characterized using the p53 gene as the model target DNA. The proposed system showed an improved assay performance due to the introduction of IGQ-structure into fluorescent signaling probes, which could inhibit the background fluorescence and increase fluorescence restoration amplitude of fluoresceins upon target DNA hybridization. The proof-of-concept scheme is expected to provide new insight into the potential of G-quadruplex structure and promote the application of fluorescent oligonucleotide probes in fundamental research, diagnosis, and treatment of genetic diseases. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Intermolecular crosslinks mediate aggregation of phospholipid vesicles by pulmonary surfactant-associated protein SAP-35

    International Nuclear Information System (INIS)

    Ross, G.R.; Sawyer, J.; Whitsett, J.

    1987-01-01

    Pulmonary surfactant-associated protein, Mr=35,000 (SAP-35) is known to bind phospholipids and is hypothesized to function in the organization of surfactant lipid membranes. SAP-35 has been observed to accelerate the calcium-induced aggregation of phospholipid vesicles. In order to define the molecular domains of SAP-35 which function in phospholipid aggregation, they have measured the light scattering properties (400nm) of purified canine SAP-35-phospholipid vesicle suspensions. Accelerated aggregation of unilamellar vesicles, requires SAP-35 and at least 2mM free calcium. The initial rate of A 400 change is proportional to the amount of native SAP-35 added over lipid:protein molar ratios ranging from 100:1 to 5000:1. Removal of the SAP-35 collagen-like domain and a specific cysteine residue involved in intermolecular disulfide bonding by bacterial collagenase digestion destroys the protein's lipid aggregation activity. Pre-incubation of SAP-35 with dithiothreitol (DTT) under nondenaturing conditions also results in a time-dependent loss of aggregation activity. Sucrose density gradient floatation of SAP-35 with 14 C dipalmitoyl phosphatidycholine labelled vesicles in the absence or presence of DTT suggests retention of SAP-35 lipid binding capacity. These data demonstrate the importance of SAP-35 triple helix and disulfide crosslinking integrity for the aggregation of unilamellar phospholipid vesicles

  3. Intermolecular Interactions in the TMEM16A Dimer Controlling Channel Activity.

    Science.gov (United States)

    Scudieri, Paolo; Musante, Ilaria; Gianotti, Ambra; Moran, Oscar; Galietta, Luis J V

    2016-12-08

    TMEM16A and TMEM16B are plasma membrane proteins with Ca 2+ -dependent Cl - channel function. By replacing the carboxy-terminus of TMEM16A with the equivalent region of TMEM16B, we obtained channels with potentiation of channel activity. Progressive shortening of the chimeric region restricted the "activating domain" to a short sequence close to the last transmembrane domain and led to TMEM16A channels with high activity at very low intracellular Ca 2+ concentrations. To elucidate the molecular mechanism underlying this effect, we carried out experiments based on double chimeras, Forster resonance energy transfer, and intermolecular cross-linking. We also modeled TMEM16A structure using the Nectria haematococca TMEM16 protein as template. Our results indicate that the enhanced activity in chimeric channels is due to altered interaction between the carboxy-terminus and the first intracellular loop in the TMEM16A homo-dimer. Mimicking this perturbation with a small molecule could be the basis for a pharmacological stimulation of TMEM16A-dependent Cl - transport.

  4. Intermolecular interaction of fosinopril with bovine serum albumin (BSA): The multi-spectroscopic and computational investigation.

    Science.gov (United States)

    Zhou, Kai-Li; Pan, Dong-Qi; Lou, Yan-Yue; Shi, Jie-Hua

    2018-04-16

    The intermolecular interaction of fosinopril, an angiotensin converting enzyme inhibitor with bovine serum albumin (BSA), has been investigated in physiological buffer (pH 7.4) by multi-spectroscopic methods and molecular docking technique. The results obtained from fluorescence and UV absorption spectroscopy revealed that the fluorescence quenching mechanism of BSA induced by fosinopril was mediated by the combined dynamic and static quenching, and the static quenching was dominant in this system. The binding constant, K b , value was found to lie between 2.69 × 10 3 and 9.55 × 10 3  M -1 at experimental temperatures (293, 298, 303, and 308 K), implying the low or intermediate binding affinity between fosinopril and BSA. Competitive binding experiments with site markers (phenylbutazone and diazepam) suggested that fosinopril preferentially bound to the site I in sub-domain IIA on BSA, as evidenced by molecular docking analysis. The negative sign for enthalpy change (ΔH 0 ) and entropy change (ΔS 0 ) indicated that van der Waals force and hydrogen bonds played important roles in the fosinopril-BSA interaction, and 8-anilino-1-naphthalenesulfonate binding assay experiments offered evidence of the involvements of hydrophobic interactions. Moreover, spectroscopic results (synchronous fluorescence, 3-dimensional fluorescence, and Fourier transform infrared spectroscopy) indicated a slight conformational change in BSA upon fosinopril interaction. Copyright © 2018 John Wiley & Sons, Ltd.

  5. Modeling the intermolecular interactions: molecular structure of N-3-hydroxyphenyl-4-methoxybenzamide.

    Science.gov (United States)

    Karabulut, Sedat; Namli, Hilmi; Kurtaran, Raif; Yildirim, Leyla Tatar; Leszczynski, Jerzy

    2014-03-01

    The title compound, N-3-hydroxyphenyl-4-methoxybenzamide (3) was prepared by the acylation reaction of 3-aminophenol (1) and 4-metoxybenzoylchloride (2) in THF and characterized by ¹H NMR, ¹³C NMR and elemental analysis. Molecular structure of the crystal was determined by single crystal X-ray diffraction and DFT calculations. 3 crystallizes in monoclinic P2₁/c space group. The influence of intermolecular interactions (dimerization and crystal packing) on molecular geometry has been evaluated by calculations performed for three different models; monomer (3), dimer (4) and dimer with added unit cell contacts (5). Molecular structure of 3, 4 and 5 was optimized by applying B3LYP method with 6-31G+(d,p) basis set in gas phase and compared with X-ray crystallographic data including bond lengths, bond angles and selected dihedral angles. It has been concluded that although the crystal packing and dimerization have a minor effect on bond lengths and angles, however, these interactions are important for the dihedral angles and the rotational conformation of aromatic rings. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. "Precipitation on Nanoparticles": Attractive Intermolecular Interactions Stabilize Specific Ligand Ratios on the Surfaces of Nanoparticles.

    Science.gov (United States)

    Chu, Zonglin; Han, Yanxiao; Kral, Petr; Klajn, Rafal

    2018-04-19

    Confining organic molecules to the surfaces of inorganic nanoparticles can induce intermolecular interactions between them, which can affect the composition of the mixed self-assembled monolayers obtained by co-adsorption from solution of two different molecules. Here, we study co-adsorption of two thiolated ligands-a dialkylviologen and a zwitterionic sulfobetaine-that can interact with each other electrostatically, onto gold nanoparticles. Consequently, the nanoparticles favor a narrow range of ratios of these two molecules that is largely independent of the molar ratio in solution. We show that changing the solution molar ratio of two ligands by a factor of ~5,000 affects the on-nanoparticle ratio of these ligands by only 3 times. This behavior is reminiscent of the formation of insoluble inorganic salts (e.g., AgCl), which similarly compensate positive and negative charges upon crystallizing. Our results pave the way towards developing well-defined hybrid organic-inorganic nanostructures. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. MAu2GeS4-Chalcogel (M = Co, Ni): Heterogeneous Intra- and Intermolecular Hydroamination Catalysts

    KAUST Repository

    Davaasuren, Bambar; Emwas, Abdul-Hamid M.; Rothenberger, Alexander

    2017-01-01

    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.

  12. 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.

  13. New insights into the dual fluorescence of methyl salicylate: effects of intermolecular hydrogen bonding and solvation.

    Science.gov (United States)

    Zhou, Panwang; Hoffmann, Mark R; Han, Keli; He, Guozhong

    2015-02-12

    In this paper, we propose a new and complete mechanism for dual fluorescence of methyl salicylate (MS) under different conditions using a combined experimental (i.e., steady-state absorption and emission spectra and time-resolved fluorescence spectra) and theoretical (i.e., time-dependent density function theory) study. First, our theoretical study indicates that the barrier height for excited state intramolecular proton transfer (ESIPT) reaction of ketoB depends on the solvent polarity. In nonpolar solvents, the ESIPT reaction of ketoB is barrierless; the barrier height will increase with increasing solvent polarity. Second, we found that, in alcoholic solvents, intermolecular hydrogen bonding plays a more important role. The ketoB form of MS can form two hydrogen bonds with alcoholic solvents; one will facilitate ESIPT and produce the emission band in the blue region; the other one precludes ESIPT and produces the emission band in the near-UV region. Our proposed new mechanism can well explain previous results as well as our new experimental results.

  14. Towards interpretation of intermolecular paramagnetic relaxation enhancement outside the fast exchange limit.

    Science.gov (United States)

    Ceccon, Alberto; Marius Clore, G; Tugarinov, Vitali

    2016-09-01

    In an exchanging system between major and minor species, the transverse paramagnetic relaxation enhancement rate observed on the resonances of the major species (Γ 2 (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 ex between the species is fast on the PRE time scale (k ex ≫ Γ2). 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(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 ex ≫ Γ2) the ratio of the apparent proton to carbon methyl PREs, ((1)Hm-Γ 2 (app) )/((13)Cm-Γ 2 (app) ), is equal to the square of the ratio of the gyromagnetic ratios of the two nuclei, (γΗ/γC)(2). However, outside the fast exchange regime, under intermediate exchange conditions (e.g. when Γ2 is comparable in magnitude to k ex) the ((1)Hm-Γ 2 (app) )/((13)Cm-Γ 2 (app) ) ratio provides a reliable measure of the 'true' methyl PREs.

  15. The study of intermolecular interactions in NLO crystal melaminium chloride hemihydrate using DFT simulation and Hirshfeld surface analysis

    Science.gov (United States)

    Sangeetha, K.; Kumar, V. R. Suresh; Marchewka, M. K.; Binoy, J.

    2018-05-01

    Since, the intermolecular interactions play a crucial role in the formation of crystalline network, its analysis throws light on structure dependent crystalline properties. In the present study, DFT based vibrational spectral investigation has been performed in the stretching region (3500 cm-1 - 2800 cm-1) of IR and Raman spectra of melaminium chloride hemihydrates. The intermolecular interaction has been investigated by analyzing the half width of the OH and NH stretching profile of the deconvoluted spectra. Correlation of vibrational spectra with Hirshfeld surface analysis and finger print plot has been contemplated and molecular docking studies has been performed on melaminium chloride hemihydrate to assess its role in the drug transport mechanism and toxicity to human body.

  16. Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study.

    Science.gov (United States)

    Meng, Qingxi; Shen, Wei; Li, Ming

    2012-03-01

    Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is -110 kJ mol(-1). Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium-alkene-benzaldehyde complex M1, rhodium-alkene-hydrogen-acyl complex M2, rhodium-alkyl-acyl complex M3, rhodium-alkyl-carbonyl-phenyl complex M4, rhodium-acyl-phenyl complex M5, and rhodium-ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart's experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp' (Cp' = C(5)Me(4)CF(3)) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

  17. 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.

  18. Resonance energy transfer (RET)-Induced intermolecular pairing force: a tunable weak interaction and its application in SWNT separation.

    Science.gov (United States)

    Pan, Xiaoyong; Chen, Hui; Wang, Wei Zhi; Ng, Siu Choon; Chan-Park, Mary B

    2011-07-21

    This paper explores evidence of an optically mediated interaction that is active in the separation mechanism of certain selective agents through consideration of the contrasting selective behaviors of two conjugated polymers with distinct optical properties. The involvement of a RET-induced intermolecular pairing force is implied by the different illumination response behaviors. The magnitude of this interaction scales with the external stimulus parameter, the illumination irradiance (I), and thus is tunable. This suggests a facile technique to modify the selectivity of polymers toward specific SWNT species by altering the polymer structure to adjust the corresponding intermolecular interaction. This is the first experimental verification and application of a RET-induced intermolecular pairing force to SWNT separation. With this kind of interaction taken into account, reasonable interpretation of some conflicting data, especially PLE maps, can be easily made. The above conclusion can be applied to other substances as long as they are electrically neutral and there is photon-induced RET between them. The significant magnitude of this interaction makes direct manipulation of molecules/particles possible and is expected to have applications in molecular engineering. © 2011 American Chemical Society

  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. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    2015-01-01

    We study possible motivations for co-entreprenurial couples to start up a joint firm, using a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and post-dissolution private and financial outcomes...

  2. Electrochemistry of transition metal complex catalysts Part 10. Intra- and intermolecular electrochemically activated C-H addition to the central metal atom of a P-C-P-pincer iridium complex

    International Nuclear Information System (INIS)

    Novak, Filip; Speiser, Bernd; Mohammad, Hani A.Y.; Mayer, Hermann A.

    2004-01-01

    The electrochemical properties of a promising catalyst for C-H bond activation are investigated. This P-C-P-pincer complex of iridium exhibits an intramolecular C-H oxidative addition at room temperature, which becomes enhanced upon oxidation. The reaction product is detected by cyclic voltammetry. Mechanistic, kinetic, and thermodynamic information is extracted from experiments in combination with digital simulation. Multicycle voltammograms and voltammograms of mixtures consistently suggest an extended square scheme as the electrode reaction mechanism. The unsubstituted parent compound shows a more complex redox behavior including a coupled ECE sequence. Intermolecular C-H activation by reaction of the complex in the presence of cyclooctane is indicated by characteristic changes in the cyclic voltammograms

  3. 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

  4. 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

  5. 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

  6. 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.

  7. Towards interpretation of intermolecular paramagnetic relaxation enhancement outside the fast exchange limit

    International Nuclear Information System (INIS)

    Ceccon, Alberto; Marius Clore, G.; Tugarinov, Vitali

    2016-01-01

    In an exchanging system between major and minor species, the transverse paramagnetic relaxation enhancement rate observed on the resonances of the major species (Γ_2"a"p"p) 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_e_x between the species is fast on the PRE time scale (k_e_x ≫ Γ_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"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_e_x ≫ Γ_2) the ratio of the apparent proton to carbon methyl PREs, ("1H_m–Γ_2"a"p"p)/("1"3C_m–Γ_2"a"p"p), is equal to the square of the ratio of the gyromagnetic ratios of the two nuclei, (γ_Η/γ_C)"2. However, outside the fast exchange regime, under intermediate exchange conditions (e.g. when Γ_2 is comparable in magnitude to k_e_x) the ("1H_m–Γ_2"a"p"p)/("1"3C_m–Γ_2"a"p"p) ratio provides a reliable measure of the ‘true’ methyl PREs.

  8. 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...

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

    DEFF Research Database (Denmark)

    Andersen, Jonas; Heimdal, J.; Wallin Mahler Andersen, Denise

    2014-01-01

    have been assigned and provide crucial observables for benchmark theoretical descriptions of this systems’ flat intermolecular potential energy surface. A (semi)-empirical value for the zero-point energy of 273 ± 15 cm−1 from the class of intermolecular van der Waals vibrations is proposed...... and the combination with high-level quantum chemical calculations provides a value of 726 ± 15 cm−1 for the dissociation energy D0...

  10. Contrasting intermolecular and intramolecular exciplex formation of a 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad.

    Science.gov (United States)

    Imoto, Mitsutaka; Ikeda, Hiroshi; Fujii, Takayuki; Taniguchi, Hisaji; Tamaki, Akihiro; Takeda, Motonori; Mizuno, Kazuhiko

    2010-05-07

    An intramolecular exciplex is formed upon excitation of the cyclohexane solution of the 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad, but little if any intramolecular CT complex exists in the ground state of this substance in solution. In contrast, in the crystalline state, the dyad forms an intermolecular mixed-stack CT complex in the ground state and an intermolecular exciplex when it is photoexcited.

  11. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    with a selected set of comparable firms and couples. We find evidence that couples often establish a business together because one spouse – most commonly the female – has limited outside opportunities in the labor market. However, the financial benefits for each of the spouses, and especially the female......We study possible motivations for co-entrepenurial couples to start up a joint firm, using a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and postdissolution private and financial outcomes......, are larger in co-entrepreneurial firms, both during the life of the business and post-dissolution. The start-up of co-entrepreneurial firms seems therefore a sound investment in the human capital of both spouses as well as in the reduction of income inequality in the household. We find no evidence of non...

  12. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    with a selected set of comparable firms and couples. We find evidence that couples often establish a business together because one spouse - most commonly the female - has limited outside opportunities in the labor market. However, the financial benefits for each of the spouses, and especially the female......We study possible motivations for co-entrepenurial couples to start up a joint firm, us-ing a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and post-dissolution private and financial outcomes......, are larger in co-entrepreneurial firms, both during the life of the business and post-dissolution. The start-up of co-entrepreneurial firms seems therefore a sound in-vestment in the human capital of both spouses as well as in the reduction of income inequality in the household. We find no evidence of non...

  13. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

    Science.gov (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun

    2017-12-01

    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

  14. Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Monahan, Daniele M.; Whaley-Mayda, Lukas; Fleming, Graham R., E-mail: grfleming@lbl.gov [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 (United States); Ishizaki, Akihito [Institute for Molecular Science, National Institutes of Natural Sciences, Okazaki 444-8585 (Japan)

    2015-08-14

    Coherence oscillations measured in two-dimensional (2D) electronic spectra of pigment-protein complexes may have electronic, vibrational, or mixed-character vibronic origins, which depend on the degree of electronic-vibrational mixing. Oscillations from intrapigment vibrations can obscure the inter-site coherence lifetime of interest in elucidating the mechanisms of energy transfer in photosynthetic light-harvesting. Huang-Rhys factors (S) for low-frequency vibrations in Chlorophyll and Bacteriochlorophyll are quite small (S ≤ 0.05), so it is often assumed that these vibrations influence neither 2D spectra nor inter-site coherence dynamics. In this work, we explore the influence of S within this range on the oscillatory signatures in simulated 2D spectra of a pigment heterodimer. To visualize the inter-site coherence dynamics underlying the 2D spectra, we introduce a formalism which we call the “site-probe response.” By comparing the calculated 2D spectra with the site-probe response, we show that an on-resonance vibration with Huang-Rhys factor as small as S = 0.005 and the most strongly coupled off-resonance vibrations (S = 0.05) give rise to long-lived, purely vibrational coherences at 77 K. We moreover calculate the correlation between optical pump interactions and subsequent entanglement between sites, as measured by the concurrence. At 77 K, greater long-lived inter-site coherence and entanglement appear with increasing S. This dependence all but vanishes at physiological temperature, as environmentally induced fluctuations destroy the vibronic mixing.

  15. Structural analysis of intermolecular interactions in the kinesin adaptor complex fasciculation and elongation protein zeta 1/ short coiled-coil protein (FEZ1/SCOCO.

    Directory of Open Access Journals (Sweden)

    Marcos Rodrigo Alborghetti

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

  16. 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

  17. A simple and reliable approach to docking protein-protein complexes from very sparse NOE-derived intermolecular distance restraints

    International Nuclear Information System (INIS)

    Tang, Chun; Clore, G. Marius

    2006-01-01

    A simple and reliable approach for docking protein-protein complexes from very sparse NOE-derived intermolecular distance restraints (as few as three from a single point) in combination with a novel representation for an attractive potential between mapped interaction surfaces is described. Unambiguous assignments of very sparse intermolecular NOEs are obtained using a reverse labeling strategy in which one the components is fully deuterated with the exception of selective protonation of the δ-methyl groups of isoleucine, while the other component is uniformly 13 C-labeled. This labeling strategy can be readily extended to selective protonation of Ala, Leu, Val or Met. The attractive potential is described by a 'reduced' radius of gyration potential applied specifically to a subset of interfacial residues (those with an accessible surface area ≥ 50% in the free proteins) that have been delineated by chemical shift perturbation. Docking is achieved by rigid body minimization on the basis of a target function comprising the sparse NOE distance restraints, a van der Waals repulsion potential and the 'reduced' radius of gyration potential. The method is demonstrated for two protein-protein complexes (EIN-HPr and IIA Glc -HPr) from the bacterial phosphotransferase system. In both cases, starting from 100 different random orientations of the X-ray structures of the free proteins, 100% convergence is achieved to a single cluster (with near identical atomic positions) with an overall backbone accuracy of ∼2 A. The approach described is not limited to NMR, since interfaces can also be mapped by alanine scanning mutagenesis, and sparse intermolecular distance restraints can be derived from double cycle mutagenesis, cross-linking combined with mass spectrometry, or fluorescence energy transfer

  18. A simple and reliable approach to docking protein-protein complexes from very sparse NOE-derived intermolecular distance restraints

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Chun; Clore, G. Marius [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)], E-mail: mariusc@intra.niddk.nih.gov

    2006-09-15

    A simple and reliable approach for docking protein-protein complexes from very sparse NOE-derived intermolecular distance restraints (as few as three from a single point) in combination with a novel representation for an attractive potential between mapped interaction surfaces is described. Unambiguous assignments of very sparse intermolecular NOEs are obtained using a reverse labeling strategy in which one the components is fully deuterated with the exception of selective protonation of the {delta}-methyl groups of isoleucine, while the other component is uniformly {sup 13}C-labeled. This labeling strategy can be readily extended to selective protonation of Ala, Leu, Val or Met. The attractive potential is described by a 'reduced' radius of gyration potential applied specifically to a subset of interfacial residues (those with an accessible surface area {>=} 50% in the free proteins) that have been delineated by chemical shift perturbation. Docking is achieved by rigid body minimization on the basis of a target function comprising the sparse NOE distance restraints, a van der Waals repulsion potential and the 'reduced' radius of gyration potential. The method is demonstrated for two protein-protein complexes (EIN-HPr and IIA{sup Glc}-HPr) from the bacterial phosphotransferase system. In both cases, starting from 100 different random orientations of the X-ray structures of the free proteins, 100% convergence is achieved to a single cluster (with near identical atomic positions) with an overall backbone accuracy of {approx}2 A. The approach described is not limited to NMR, since interfaces can also be mapped by alanine scanning mutagenesis, and sparse intermolecular distance restraints can be derived from double cycle mutagenesis, cross-linking combined with mass spectrometry, or fluorescence energy transfer.

  19. Intermolecular interactions in aqueous solutions of gallic acid at 296-306 K according to spectrofluorimetry and densimetry data

    Science.gov (United States)

    Grigoryan, K. R.; Sargsyan, L. S.

    2015-12-01

    Features of intermolecular interactions in aqueous solutions of gallic acid (GA) are studied by means of densimetry and fluorescence spectroscopy (intrinsic fluorescence, 2D spectra, and excitation/ emission matrix fluorescence spectra, 3D) at 296.15, 301.15, and 306.15 K in the concentration range of 5.88 × 10-4-5.88 × 10-2 mol L-1. It is shown by analyzing the concentration and temperature dependences of the apparent molar volumes and fluorescence parameters of GA that the equilibrium between nonassociated and associated species in the solution and the hydration of these species undergo changes.

  20. Iron(II)-catalyzed intermolecular amino-oxygenation of olefins through the N-O bond cleavage of functionalized hydroxylamines.

    Science.gov (United States)

    Lu, Deng-Fu; Zhu, Cheng-Liang; Jia, Zhen-Xin; Xu, Hao

    2014-09-24

    An iron-catalyzed diastereoselective intermolecular olefin amino-oxygenation reaction is reported, which proceeds via an iron-nitrenoid generated by the N-O bond cleavage of a functionalized hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative is used as the amination reagent and oxidant. This method tolerates a range of synthetically valuable substrates that have been all incompatible with existing amino-oxygenation methods. It can also provide amino alcohol derivatives with regio- and stereochemical arrays complementary to known amino-oxygenation methods.

  1. Organophotocatalysis: Insights into the Mechanistic Aspects of Thiourea-Mediated Intermolecular [2+2] Photocycloadditions.

    Science.gov (United States)

    Vallavoju, Nandini; Selvakumar, Sermadurai; Pemberton, Barry C; Jockusch, Steffen; Sibi, Mukund P; Sivaguru, Jayaraman

    2016-04-25

    Mechanistic investigations of the intermolecular [2+2] photocycloaddition of coumarin with tetramethylethylene mediated by thiourea catalysts reveal that the reaction is enabled by a combination of minimized aggregation, enhanced intersystem crossing, and altered excited-state lifetime(s). These results clarify how the excited-state reactivity can be manipulated through catalyst-substrate interactions and reveal a third mechanistic pathway for thiourea-mediated organo-photocatalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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

  3. 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

  4. Solvation study of the non-specific lipid transfer protein from wheat by intermolecular NOEs with water and small organic molecules

    International Nuclear Information System (INIS)

    Liepinsh, Edvards; Sodano, Patrick; Tassin, Severine; Marion, Didier; Vovelle, Francoise; Otting, Gottfried

    1999-01-01

    Intermolecular nuclear Overhauser effects (NOEs) were measured between the protons of various small solvent or gas molecules and the non-specific lipid transfer protein (ns-LTP) from wheat. Intermolecular NOEs were observed with the hydrophobic pocket in the interior of wheat ns-LTP, which grew in intensity in the order cyclopropane (saturated solution) < methane (140 bar) < ethane (40 bar) < acetonitrile (5% in water) < cyclohexane (saturated solution) < benzene (saturated solution). No intermolecular NOEs were observed with dioxane (5% in water). The intermolecular NOEs were negative for all of the organic molecules tested. Intermolecular NOEs between wheat ns-LTP and water were weak or could not be distinguished from exchange-relayed NOEs. As illustrated by the NOEs with cyclohexane versus dioxane, the hydrophobic pocket in wheat ns-LTP preferably binds non-polar molecules. Yet, polar molecules like acetonitrile can also be accommodated. The pressure dependence of the NOEs between methane and wheat ns-LTP indicated incomplete occupancy, even at 190 bar methane pressure. In general, NOE intensities increased with the size of the ligand molecule and its vapor pressure. NMR of the vapor phase showed excellent resolution between the signals from the gas phase and those from the liquid phase. The vapor concentration of cyclohexane was fivefold higher than that of the dioxane solution, supporting the binding of cyclohexane versus uptake of dioxane

  5. 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.

  6. Photoinduced intermolecular electron transfer and off-resonance Raman characteristics of Rhodamine 101/N,N-diethylaniline

    International Nuclear Information System (INIS)

    Jiang, Li-lin; Liu, Wei-long; Song, Yun-fei; He, Xing; Wang, Yang; Wang, Chang; Wu, Hong-lin; Yang, Fang; Yang, Yan-qiang

    2014-01-01

    Highlights: • Mechanism of PIET reaction process for the Rh101 + /DEA system is investigated. • The significant geometrical changes of the charge–transfer complex are explained. • Forward Electron transfer from DEA to Rh101 +∗ occurs with lifetime of 425–560 fs. • Backward electron transfer occurs with a time constant of 46.16–51.40 ps. • Intramolecular vibrational relaxation occurs with lifetime of 2.77–5.39 ps. - Abstract: The ultrafast photoinduced intermolecular electron transfer (PIET) reaction of Rhodamine 101 (Rh101 + ) in N,N-diethylaniline (DEA) was investigated using off-resonance Raman, femtosecond time-resolved multiplex transient grating (TG) and transient absorption (TA) spectroscopies. The Raman spectra indicate that the C=C stretching vibration of the chromophore aromatic ring is more sensitive to ET compared with the C-C stretching mode. The ultrafast photoinduced intermolecular forward ET (FET) from DEA to Rh101 +∗ occurs on a time scale of τ FET = 425–560 fs. The backward ET (BET) occurs in the inverted region with a time constant of τ BET = 46.16–51.40 ps. The intramolecular vibrational relaxation (IVR) process occurs on the excited state potential energy surface with the time constant of τ IVR = 2.77–5.39 ps

  7. 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

  8. Photoinduced intermolecular electron transfer and off-resonance Raman characteristics of Rhodamine 101/N,N-diethylaniline

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Li-lin [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); School of Mechanical and Electronic Engineering, Hezhou University, Hezhou 542800 (China); Liu, Wei-long; Song, Yun-fei; He, Xing; Wang, Yang; Wang, Chang; Wu, Hong-lin [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); Yang, Fang [National Key Laboratory of Science and Technology on Tunable Laser, Department of Optoelectronics Information Science Technology, Harbin Institute of Technology, Harbin 150001 (China); Yang, Yan-qiang, E-mail: yqyang@hit.edu.cn [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics, Mianyang 621900, Sichuan (China)

    2014-01-31

    Highlights: • Mechanism of PIET reaction process for the Rh101{sup +}/DEA system is investigated. • The significant geometrical changes of the charge–transfer complex are explained. • Forward Electron transfer from DEA to Rh101{sup +∗} occurs with lifetime of 425–560 fs. • Backward electron transfer occurs with a time constant of 46.16–51.40 ps. • Intramolecular vibrational relaxation occurs with lifetime of 2.77–5.39 ps. - Abstract: The ultrafast photoinduced intermolecular electron transfer (PIET) reaction of Rhodamine 101 (Rh101{sup +}) in N,N-diethylaniline (DEA) was investigated using off-resonance Raman, femtosecond time-resolved multiplex transient grating (TG) and transient absorption (TA) spectroscopies. The Raman spectra indicate that the C=C stretching vibration of the chromophore aromatic ring is more sensitive to ET compared with the C-C stretching mode. The ultrafast photoinduced intermolecular forward ET (FET) from DEA to Rh101{sup +∗} occurs on a time scale of τ{sub FET} = 425–560 fs. The backward ET (BET) occurs in the inverted region with a time constant of τ{sub BET} = 46.16–51.40 ps. The intramolecular vibrational relaxation (IVR) process occurs on the excited state potential energy surface with the time constant of τ{sub IVR} = 2.77–5.39 ps.

  9. Metal-Catalyzed Intra- and Intermolecular Addition of Carboxylic Acids to Alkynes in Aqueous Media: A Review

    Directory of Open Access Journals (Sweden)

    Javier Francos

    2017-11-01

    Full Text Available The metal-catalyzed addition of carboxylic acids to alkynes is a very effective tool for the synthesis of carboxylate-functionalized olefinic compounds in an atom-economical manner. Thus, a large variety of synthetically useful lactones and enol-esters can be accessed through the intra- or intermolecular versions of this process. In order to reduce the environmental impact of these reactions, considerable efforts have been devoted in recent years to the development of catalytic systems able to operate in aqueous media, which represent a real challenge taking into account the tendency of alkynes to undergo hydration in the presence of transition metals. Despite this, different Pd, Pt, Au, Cu and Ru catalysts capable of promoting the intra- and intermolecular addition of carboxylic acids to alkynes in a selective manner in aqueous environments have appeared in the literature. In this review article, an overview of this chemistry is provided. The synthesis of β-oxo esters by catalytic addition of carboxylic acids to terminal propargylic alcohols in water is also discussed.

  10. Effect of intermolecular dipole-dipole interactions on interfacial supramolecular structures of C3-symmetric hexa-peri-hexabenzocoronene derivatives.

    Science.gov (United States)

    Mu, Zhongcheng; Shao, Qi; Ye, Jun; Zeng, Zebing; Zhao, Yang; Hng, Huey Hoon; Boey, Freddy Yin Chiang; Wu, Jishan; Chen, Xiaodong

    2011-02-15

    Two-dimensional (2D) supramolecular assemblies of a series of novel C(3)-symmetric hexa-peri-hexabenzocoronene (HBC) derivatives bearing different substituents adsorbed on highly oriented pyrolytic graphite were studied by using scanning tunneling microscopy at a solid-liquid interface. It was found that the intermolecular dipole-dipole interactions play a critical role in controlling the interfacial supramolecular assembly of these C(3)-symmetric HBC derivatives at the solid-liquid interface. The HBC molecule bearing three -CF(3) groups could form 2D honeycomb structures because of antiparallel dipole-dipole interactions, whereas HBC molecules bearing three -CN or -NO(2) groups could form hexagonal superstructures because of a special trimeric arrangement induced by dipole-dipole interactions and weak hydrogen bonding interactions ([C-H···NC-] or [C-H···O(2)N-]). Molecular mechanics and dynamics simulations were performed to reveal the physics behind the 2D structures as well as detailed functional group interactions. This work provides an example of how intermolecular dipole-dipole interactions could enable fine control over the self-assembly of disklike π-conjugated molecules.

  11. Influence of intermolecular amide hydrogen bonding on the geometry, atomic charges, and spectral modes of acetanilide: An ab initio study

    Science.gov (United States)

    Binoy, J.; Prathima, N. B.; Murali Krishna, C.; Santhosh, C.; Hubert Joe, I.; Jayakumar, V. S.

    2006-08-01

    Acetanilide, a compound of pharmaceutical importance possessing pain-relieving properties due to its blocking the pulse dissipating along the nerve fiber, is subjected to vibrational spectral investigation using NIR FT Raman, FT-IR, and SERS. The geometry, Mulliken charges, and vibrational spectrum of acetanilide have been computed using the Hartree-Fock theory and density functional theory employing the 6-31G (d) basis set. To investigate the influence of intermolecular amide hydrogen bonding, the geometry, charge distribution, and vibrational spectrum of the acetanilide dimer have been computed at the HF/6-31G (d) level. The computed geometries reveal that the acetanilide molecule is planar, while twisting of the secondary amide group with respect to the phenyl ring is found upon hydrogen bonding. The trans isomerism and “amido” form of the secondary amide, hyperconjugation of the C=O group with the adjacent C-C bond, and donor-acceptor interaction have been investigated using computed geometry. The carbonyl stretching band position is found to be influenced by the tendency of the phenyl ring to withdraw nitrogen lone pair, intermolecular hydrogen bonding, conjugation, and hyperconjugation. A decrease in the NH and C=O bond orders and increase in the C-N bond orders due to donor-acceptor interaction can be observed in the vibrational spectra. The SERS spectral analysis reveals that the flat orientation of the molecule on the adsorption plane is preferred.

  12. Exchange coupling and magnetic anisotropy of exchanged-biased quantum tunnelling single-molecule magnet Ni3Mn2 complexes using theoretical methods based on Density Functional Theory.

    Science.gov (United States)

    Gómez-Coca, Silvia; Ruiz, Eliseo

    2012-03-07

    The magnetic properties of a new family of single-molecule magnet Ni(3)Mn(2) complexes were studied using theoretical methods based on Density Functional Theory (DFT). The first part of this study is devoted to analysing the exchange coupling constants, focusing on the intramolecular as well as the intermolecular interactions. The calculated intramolecular J values were in excellent agreement with the experimental data, which show that all the couplings are ferromagnetic, leading to an S = 7 ground state. The intermolecular interactions were investigated because the two complexes studied do not show tunnelling at zero magnetic field. Usually, this exchange-biased quantum tunnelling is attributed to the presence of intermolecular interactions calculated with the help of theoretical methods. The results indicate the presence of weak intermolecular antiferromagnetic couplings that cannot explain the ferromagnetic value found experimentally for one of the systems. In the second part, the goal is to analyse magnetic anisotropy through the calculation of the zero-field splitting parameters (D and E), using DFT methods including the spin-orbit effect.

  13. Temperature-dependent conformations of exciton-coupled Cy3 dimers in double-stranded DNA

    Science.gov (United States)

    Kringle, Loni; Sawaya, Nicolas P. D.; Widom, Julia; Adams, Carson; Raymer, Michael G.; Aspuru-Guzik, Alán; Marcus, Andrew H.

    2018-02-01

    Understanding the properties of electronically interacting molecular chromophores, which involve internally coupled electronic-vibrational motions, is important to the spectroscopy of many biologically relevant systems. Here we apply linear absorption, circular dichroism, and two-dimensional fluorescence spectroscopy to study the polarized collective excitations of excitonically coupled cyanine dimers (Cy3)2 that are rigidly positioned within the opposing sugar-phosphate backbones of the double-stranded region of a double-stranded (ds)-single-stranded (ss) DNA fork construct. We show that the exciton-coupling strength of the (Cy3)2-DNA construct can be systematically varied with temperature below the ds-ss DNA denaturation transition. We interpret spectroscopic measurements in terms of the Holstein vibronic dimer model, from which we obtain information about the local conformation of the (Cy3)2 dimer, as well as the degree of static disorder experienced by the Cy3 monomer and the (Cy3)2 dimer probe locally within their respective DNA duplex environments. The properties of the (Cy3)2-DNA construct we determine suggest that it may be employed as a useful model system to test fundamental concepts of protein-DNA interactions and the role of electronic-vibrational coherence in electronic energy migration within exciton-coupled bio-molecular arrays.

  14. Ab initio calculations on the X (2)B1 and A (2)A1 states of AsH2, and Franck-Condon simulation, including anharmonicity, of the A(0,0,0)-X single vibronic level emission spectrum of AsH2.

    Science.gov (United States)

    Lee, Edmond P F; Mok, Daniel K W; Chau, Foo-Tim; Dyke, John M

    2010-06-21

    Restricted-spin coupled-cluster single-double plus perturbative triple excitation {RCCSD(T)} calculations were carried out on the X (2)B(1) and A (2)A(1) states of AsH(2) employing the fully relativistic small-core effective core potential (ECP10MDF) for As and basis sets of up to the augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality. Minimum-energy geometrical parameters and relative electronic energies were evaluated, including contributions from extrapolation to the complete basis set limit and from outer core correlation of the As 3d(10) electrons employing additional tight 4d3f2g2h functions designed for As. In addition, simplified, explicitly correlated CCSD(T)-F12 calculations were also performed employing different atomic orbital basis sets of up to aug-cc-pVQZ quality, and associated complementary auxiliary and density-fitting basis sets. The best theoretical estimate of the relative electronic energy of the A (2)A(1) state of AsH(2) relative to the X (2)B(1) state including zero-point energy correction (T(0)) is 19,954(32) cm(-1), which agrees very well with available experimental T(0) values of 19,909.4531(18) and 19,909.4910(17) cm(-1) obtained from recent laser induced fluorescence and cavity ringdown absorption spectroscopic studies. In addition, potential energy functions (PEFs) of the X (2)B(1) and A (2)A(1) states of AsH(2) were computed at different RCCSD(T) and CCSD(T)-F12 levels. These PEFs were used in variational calculations of anharmonic vibrational wave functions, which were then utilized to calculate Franck-Condon factors (FCFs) between these two states, using a method which includes allowance for anharmonicity and Duschinsky rotation. The A(0,0,0)-X single vibronic level (SVL) emission spectrum of AsH(2) was simulated using these computed FCFs. Comparison between simulated and available experimental vibrationally resolved spectra of the A(0,0,0)-X SVL emission of AsH(2), which consist essentially of

  15. 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.

  16. An Efficient Method to Evaluate Intermolecular Interaction Energies in Large Systems Using Overlapping Multicenter ONIOM and the Fragment Molecular Orbital Method

    Science.gov (United States)

    Asada, Naoya; Fedorov, Dmitri G.; Kitaura, Kazuo; Nakanishi, Isao; Merz, Kenneth M.

    2012-01-01

    We propose an approach based on the overlapping multicenter ONIOM to evaluate intermolecular interaction energies in large systems and demonstrate its accuracy on several representative systems in the complete basis set limit at the MP2 and CCSD(T) level of theory. In the application to the intermolecular interaction energy between insulin dimer and 4′-hydroxyacetanilide at the MP2/CBS level, we use the fragment molecular orbital method for the calculation of the entire complex assigned to the lowest layer in three-layer ONIOM. The developed method is shown to be efficient and accurate in the evaluation of the protein-ligand interaction energies. PMID:23050059

  17. Two alternative derivations of the static contribution to the radiation-induced intermolecular energy shift

    International Nuclear Information System (INIS)

    Salam, A.

    2007-01-01

    Two contrasting physical viewpoints and calculational approaches are adopted within the framework of molecular quantum electrodynamics for the evaluation of the static contribution to the change in mutual interaction energy between a pair of electric dipole polarizable molecules in an intense radiation field. This term arises when a real photon is scattered by the same molecular center with coupling between the two bodies occurring via exchange of a single virtual photon. In one method it is found that utilization of an effective three-photon interaction operator enables the energy shift to be obtained using second order perturbation theory with summation over only four time-ordered diagrams, each of which contain collapsed interaction vertices. The result is then shown to be obtained even more easily in a second approach that involves calculating the expectation values for both molecules in the ground electronic state and the field containing N photons of mode (k-vector,λ) of the electric dipole moments induced at each molecule by the incident field, which are coupled to the resonant dipole-dipole interaction tensor. The static contribution in question is shown to arise from the interaction of a permanent electric dipole moment in one species with the first hyperpolarizability of the other. Both methods are compared and contrasted with a previous computation in which contributions to the energy shift arising from 48 time-ordered diagrams were summed using fourth order perturbation theory

  18. 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

  19. Symmetric bi-pyridyl banana-shaped molecule and its intermolecular hydrogen bonding liquid-crystalline complexes

    Science.gov (United States)

    Sui, Dan; Hou, Qiufei; Chai, Jia; Ye, Ling; Zhao, Liyan; Li, Min; Jiang, Shimei

    2008-11-01

    A new symmetric bi-pyridyl banana-shaped molecule 1,3-phenylene diisonicotinate (PDI) was designed and synthesized. Its molecular structure was confirmed by FTIR, Elemental analysis and 1H NMR. X-ray crystallographic study reveals that there is an angle of approximate 118° among the centroids of the three rings (pyridyl-phenyl-pyridyl) in each PDI molecule indicating a desired banana shape. In addition, a series of liquid crystal complexes nBA:PDI:nBA induced by intermolecular hydrogen bonding between PDI (proton acceptor) and 4-alkoxybenzoic acids (nBA, proton donor) were synthesized and characterized. The mesomorphism properties and optical textures of the complex of nBA:PDI:nBA were investigated by differential scanning calorimetry, polarizing optical microscope and X-ray diffraction.

  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

    2017-10-05

    The interaction between berberine chloride and β-cyclodextrin (β-CyD) is investigated via 2D asynchronous UV-Vis spectrum. The occurrence of cross peaks around (420nm, 420nm) 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 420nm band of berberine undergoes a red-shift, and its bandwidth decreases under the interaction with β-CyD. The red-shift of the 420nm 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. Copyright © 2017. Published by Elsevier B.V.

  1. 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

  2. Rhodium(III)-Catalyzed Activation of C(sp3)-H Bonds and Subsequent Intermolecular Amidation at Room Temperature.

    Science.gov (United States)

    Huang, Xiaolei; Wang, Yan; Lan, Jingbo; You, Jingsong

    2015-08-03

    Disclosed herein is a Rh(III)-catalyzed chelation-assisted activation of unreactive C(sp3)-H bonds, thus enabling an intermolecular amidation to provide a practical and step-economic route to 2-(pyridin-2-yl)ethanamine derivatives. Substrates with other N-donor groups are also compatible with the amidation. This protocol proceeds at room temperature, has a relatively broad functional-group tolerance and high selectivity, and demonstrates the potential of rhodium(III) in the promotive functionalization of unreactive C(sp3)-H bonds. A rhodacycle having a SbF6(-) counterion was identified as a plausible intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Substrate-Mediated C-C and C-H Coupling after Dehalogenation.

    Science.gov (United States)

    Kong, Huihui; Yang, Sha; Gao, Hongying; Timmer, Alexander; Hill, Jonathan P; Díaz Arado, Oscar; Mönig, Harry; Huang, Xinyan; Tang, Qin; Ji, Qingmin; Liu, Wei; Fuchs, Harald

    2017-03-15

    Intermolecular C-C coupling after cleavage of C-X (mostly, X = Br or I) bonds has been extensively studied for facilitating the synthesis of polymeric nanostructures. However, the accidental appearance of C-H coupling at the terminal carbon atoms would limit the successive extension of covalent polymers. To our knowledge, the selective C-H coupling after dehalogenation has not so far been reported, which may illuminate another interesting field of chemical synthesis on surfaces besides in situ fabrication of polymers, i.e., synthesis of novel organic molecules. By combining STM imaging, XPS analysis, and DFT calculations, we have achieved predominant C-C coupling on Au(111) and more interestingly selective C-H coupling on Ag(111), which in turn leads to selective synthesis of polymeric chains or new organic molecules.

  4. Intermolecular interactions between B. mori silk fibroin and poly(L-lactic acid) in electrospun composite nanofibrous scaffolds

    Energy Technology Data Exchange (ETDEWEB)

    Taddei, Paola, E-mail: paola.taddei@unibo.it [Dipartimento di Scienze Biomediche e Neuromotorie, Università di Bologna, Via Belmeloro 8/2, 40126 Bologna (Italy); Tozzi, Silvia [Dipartimento di Scienze Biomediche e Neuromotorie, Università di Bologna, Via Belmeloro 8/2, 40126 Bologna (Italy); Zuccheri, Giampaolo [Dipartimento di Farmacia e Biotecnologie e Centro Interdipartimentale di Ricerca Industriale Scienze della Vita e Tecnologie per la Salute, Università di Bologna, Via Irnerio 48, 40126 Bologna (Italy); Centro S3, Istituto Nanoscienze, Consiglio Nazionale delle Ricerche, Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (Italy); Martinotti, Simona; Ranzato, Elia [Dipartimento di Scienze e Innovazione Tecnologica, DiSIT, Università del Piemonte Orientale, viale Teresa Michel 11, 15121 Alessandria (Italy); Chiono, Valeria; Carmagnola, Irene [Dipartimento di Ingegneria Meccanica e Aerospaziale, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino (Italy); Tsukada, Masuhiro [Division of Applied Biology, Faculty of Textile Science and Technology, Shinshu University, 3-15-1, Tokida, Ueda, Nagano 386-8567 (Japan)

    2017-01-01

    In this study, composite nanofibrous scaffolds were obtained by electrospinning a trifluoroacetic acid solution containing B. mori silk fibroin (SF) and poly(L-lactic acid) (PLLA) in a 1:1 weight ratio. SF, PLLA and SF/PLLA nanofibres were prepared with average diameter sizes of 360 ± 90 nm, 470 ± 240 nm and 580 ± 220 nm, respectively, as assessed by SEM analysis. Vibrational and thermal analyses showed that upon blending in the SF/PLLA nanofibres, the crystallisation of PLLA was hindered by the presence of SF, which crystallized preferentially and underwent conformational changes that did not significantly change its prevailing β-sheet structure. The two components were thermodynamically compatible and the intermolecular interactions between them were revealed for the first time. Human keratinocytes were cultured on nanofibres and their viability and proliferation were determined. Preliminary in vitro tests showed that the incorporation of SF into the PLLA component enhanced cell adhesion and proliferation with respect to the unfunctionalised material. SF has been successfully used to modify the biomaterial properties and confirmed to be an efficient bioactive protein to mediate cell-biomaterial interaction. - Highlights: • Composite silk fibroin-poly(L-lactic acid) scaffolds were obtained by electrospinning. • Intermolecular interactions between SF and PLLA were revealed for the first time. • Upon blending, the crystallisation of PLLA was hindered by the presence of SF. • SF crystallized preferentially and maintained its prevailing β-sheet structure. • The incorporation of SF into PLLA enhanced human keratinocytes adhesion and proliferation.

  5. Modeling the Alzheimer Abeta17-42 fibril architecture: tight intermolecular sheet-sheet association and intramolecular hydrated cavities.

    Science.gov (United States)

    Zheng, Jie; Jang, Hyunbum; Ma, Buyong; Tsai, Chung-Jun; Nussinov, Ruth

    2007-11-01

    We investigate Abeta(17-42) protofibril structures in solution using molecular dynamics simulations. Recently, NMR and computations modeled the Abeta protofibril as a longitudinal stack of U-shaped molecules, creating an in-parallel beta-sheet and loop spine. Here we study the molecular architecture of the fibril formed by spine-spine association. We model in-register intermolecular beta-sheet-beta-sheet associations and study the consequences of Alzheimer's mutations (E22G, E22Q, E22K, and M35A) on the organization. We assess the structural stability and association force of Abeta oligomers with different sheet-sheet interfaces. Double-layered oligomers associating through the C-terminal-C-terminal interface are energetically more favorable than those with the N-terminal-N-terminal interface, although both interfaces exhibit high structural stability. The C-terminal-C-terminal interface is essentially stabilized by hydrophobic and van der Waals (shape complementarity via M35-M35 contacts) intermolecular interactions, whereas the N-terminal-N-terminal interface is stabilized by hydrophobic and electrostatic interactions. Hence, shape complementarity, or the "steric zipper" motif plays an important role in amyloid formation. On the other hand, the intramolecular Abeta beta-strand-loop-beta-strand U-shaped motif creates a hydrophobic cavity with a diameter of 6-7 A, allowing water molecules and ions to conduct through. The hydrated hydrophobic cavities may allow optimization of the sheet association and constitute a typical feature of fibrils, in addition to the tight sheet-sheet association. Thus, we propose that Abeta fiber architecture consists of alternating layers of tight packing and hydrated cavities running along the fibrillar axis, which might be possibly detected by high-resolution imaging.

  6. 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.

  7. Iodine-Catalyzed Direct Olefination of 2-Oxindoles and Alkenes via Cross-Dehydrogenative Coupling (CDC) in Air.

    Science.gov (United States)

    Huang, Hong-Yan; Wu, Hong-Ru; Wei, Feng; Wang, Dong; Liu, Li

    2015-08-07

    A direct intermolecular olefination of sp(3) C-H bond between 2-oxindoles and simple alkenes via a Cross-Dehydrogenative Coupling (CDC) strategy has been developed. In the absence of additional base, moderate to excellent yields have been obtained by using a catalytic amount of iodine with atmospheric oxygen as the reoxidant. Based on the observation of a radical capture experiment, the transformation is proposed to proceed via a radical process.

  8. Dark coupling

    International Nuclear Information System (INIS)

    Gavela, M.B.; Hernández, D.; Honorez, L. Lopez; Mena, O.; Rigolin, S.

    2009-01-01

    The two dark sectors of the universe—dark matter and dark energy—may interact with each other. Background and linear density perturbation evolution equations are developed for a generic coupling. We then establish the general conditions necessary to obtain models free from non-adiabatic instabilities. As an application, we consider a viable universe in which the interaction strength is proportional to the dark energy density. The scenario does not exhibit ''phantom crossing'' and is free from instabilities, including early ones. A sizeable interaction strength is compatible with combined WMAP, HST, SN, LSS and H(z) data. Neutrino mass and/or cosmic curvature are allowed to be larger than in non-interacting models. Our analysis sheds light as well on unstable scenarios previously proposed

  9. Molecular simulation of fluids with non-identical intermolecular potentials: Thermodynamic properties of 10-5 + 12-6 Mie potential binary mixtures

    International Nuclear Information System (INIS)

    Stiegler, Thomas; Sadus, Richard J.

    2015-01-01

    General methods for combining interactions between particles characterised by non-identical intermolecular potentials are investigated. The combination methods are tested by performing molecular dynamics simulations to determine the pressure, energy, isochoric and isobaric heat capacities, thermal expansion coefficient, isothermal compressibility, Joule-Thomson coefficient, and speed of sound of 10-5 + 12-6 Mie potential binary mixtures. In addition to the two non-identical Mie potentials, mixtures are also studied with non-identical intermolecular parameters. The combination methods are compared with results obtained by simply averaging the Mie exponents. When either the energy or size parameters are non-identical, very significant differences emerge in the thermodynamic properties predicted by the alternative combination methods. The isobaric heat capacity is the thermodynamic property that is most affected by the relative magnitude of the intermolecular potential parameters and the method for combining non-identical potentials. Either the arithmetic or geometric combination of potentials provides a simple and effective way of performing simulations involving mixtures of components characterised by non-identical intermolecular potentials, which is independent of their functional form

  10. Chemical cross-linking with thiol-cleavable reagents combined with differential mass spectrometric peptide mapping--a novel approach to assess intermolecular protein contacts

    DEFF Research Database (Denmark)

    Bennett, K L; Kussmann, M; Björk, P

    2000-01-01

    The intermolecular contact regions between monomers of the homodimeric DNA binding protein ParR and the interaction between the glycoproteins CD28 and CD80 were investigated using a strategy that combined chemical cross-linking with differential MALDI-MS analyses. ParR dimers were modified in vit...

  11. 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…

  12. Separation and Characterization of DNA Molecules and Intermolecular Interactions in Pressure-Driven Micro Flow

    Science.gov (United States)

    Friedrich, Sarah; Wang, Tza-Huei

    Pressure-driven flow in micron-sized diameter capillaries can be used to separate DNA molecules by size in a technique called Free Solution Hydrodynamic Separation. By coupling this technique with Cylindrical Illumination Confocal Spectroscopy, we have developed a highly sensitive and quantitative platform capable of separating DNA molecules by length over a large dynamic range (25 bp to 48 kbp) in a single run using only picoliters or femtograms of a DNA sample. The optical detection volume completely spans the capillary cross section, enabling highly efficient single molecule detection for enhanced sensitivity and quantification accuracy via single molecule counting. Because each DNA molecule generates its own fluorescent burst, these burst profiles can be further analyzed to individually characterize each DNA molecule's shape as it passes through the detection region. We exploit these burst profiles to visualize fluctuations in conformation under shear flow in microcapillaries, and utilizing combined mobility shift analysis, explore the complex relationship between molecular properties including length and conformation, hydrodynamic mobility, solution conditions including ion species and concentrations, and separation conditions including flow rate and capillary diameter.

  13. Spectroscopic Characterization of Intermolecular Interaction of Amyloid β Promoted on GM1 Micelles

    Directory of Open Access Journals (Sweden)

    Maho Yagi-Utsumi

    2011-01-01

    Full Text Available Clusters of GM1 gangliosides act as platforms for conformational transition of monomeric, unstructured amyloid β (Aβ to its toxic β-structured aggregates. We have previously shown that Aβ(1–40 accommodated on the hydrophobic/hydrophilic interface of lyso-GM1 or GM1 micelles assumes α-helical structures under ganglioside-excess conditions. For better understanding of the mechanisms underlying the α-to-β conformational transition of Aβ on GM1 clusters, we performed spectroscopic characterization of Aβ(1–40 titrated with GM1. It was revealed that the thioflavin T- (ThT- reactive β-structure is more populated in Aβ(1–40 under conditions where the Aβ(1–40 density on GM1 micelles is high. Under this circumstance, the C-terminal hydrophobic anchor Val39-Val40 shows two distinct conformational states that are reactive with ThT, while such Aβ species were not generated by smaller lyso-GM1 micelles. These findings suggest that GM1 clusters promote specific Aβ-Aβ interactions through their C-termini coupled with formation of the ThT-reactive β-structure depending on sizes and curvatures of the clusters.

  14. Dynamics of coupled electron-nuclei-systems in laser fields

    International Nuclear Information System (INIS)

    Falge, Mirjam

    2012-01-01

    influence of non-adiabatic effects in this asymmetry were investigated. In the last part of this work, the dynamics and optical control in spin-coupled vibronic states were analysed.

  15. Structure, stability, and thermodynamics of a short intermolecular purine-purine-pyrimidine triple helix

    International Nuclear Information System (INIS)

    Pilch, D.S.; Shafer, R.H.; Levenson, C.

    1991-01-01

    The authors have investigated the structure and physical chemistry of the d(C 3 T 4 C 3 )·2[d(G 3 A 4 G 3 )] triple helix by polyacrylamide gel electrophoresis (PAGE), 1 H NMR, and ultraviolet (UV) absorption spectroscopy. The triplex was stabilized with MgCl 2 at neutral pH. PAGE studies verify the stoichiometry of the strands comprising the triplex and indicate that the orientation of the third strand in purine-purine-pyrimidine (pur-pur-pyr) triplexes is antiparallel with respect to the purine strand of the underlying duplex. Imino proton NMR spectra provide evidence for the existence of new purine-purine (pur·pur) hydrogen bonds, in addition to those of the Watson-Crick (W-C) base pairs, in the triplex structure. These new hydrogen bonds are likely to correspond to the interaction between third-strand guanine NH1 imino protons and the N7 atoms of guanine residues on the puring strand of the underlying duplex. Thermal denaturation of the triplex proceeds to single strands in one step, under the conditions used in this study. Binding of the third strand appears to enhance the thermal stability of the duplex by 1-3 C, depending on the DNA concentration. This marked enhancement in stability, coupled with the lack of an acidic pH requirement, suggests that pur-pur-pyr triplexes are appealing choices for use in applications involving oligonucleotide targeting of duplex DNA in vitro and in vivo

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

    International Nuclear Information System (INIS)

    Pandey, Puneet Kumar; Pandey, Vrijesh Kumar; Awasthi, Anjali; Nain, Anil Kumar; Awasthi, Aashees

    2014-01-01

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

  17. 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.

  18. Force field refinement from NMR scalar couplings

    Energy Technology Data Exchange (ETDEWEB)

    Huang Jing [Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland); Meuwly, Markus, E-mail: m.meuwly@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland)

    2012-03-02

    Graphical abstract: We show that two classes of H-bonds are sufficient to quantitatively describe scalar NMR coupling constants in small proteins. Highlights: Black-Right-Pointing-Pointer We present force field refinements based on explicit MD simulations using scalar couplings across hydrogen bonds. Black-Right-Pointing-Pointer This leads to {sup h3}J{sub NC{sup }{sup P}{sup r}{sup i}{sup m}{sup e}} couplings to within 0.03 Hz at best compared to experiment. Black-Right-Pointing-Pointer A classification of H-bonds according to secondary structure is not sufficiently robust. Black-Right-Pointing-Pointer Grouping H-bonds into two classes and reparametrization yields an RMSD of 0.07 Hz. Black-Right-Pointing-Pointer This is an improvement of 50. - Abstract: NMR observables contain valuable information about the protein dynamics sampling a high-dimensional potential energy surface. Depending on the observable, the dynamics is sensitive to different time-windows. Scalar coupling constants {sup h3}J{sub NC{sup }{sup P}{sup r}{sup i}{sup m}{sup e}} reflect the pico- to nanosecond motions associated with the intermolecular hydrogen bond network. Including an explicit H-bond in the molecular mechanics with proton transfer (MMPT) potential allows us to reproduce experimentally determined {sup h3}J{sub NC{sup }{sup P}{sup r}{sup i}{sup m}{sup e}} couplings to within 0.02 Hz at best for ubiquitin and protein G. This is based on taking account of the chemically changing environment by grouping the H-bonds into up to seven classes. However, grouping them into two classes already reduces the RMSD between computed and observed {sup h3}J{sub NC{sup }{sup P}{sup r}{sup i}{sup m}{sup e}} couplings by almost 50%. Thus, using ensemble-averaged data with two classes of H-bonds leads to substantially improved scalar couplings from simulations with accurate force fields.

  19. Analysis and Ranking of Protein-Protein Docking Models Using Inter-Residue Contacts and Inter-Molecular Contact Maps

    KAUST Repository

    Oliva, Romina; Chermak, Edrisse; Cavallo, Luigi

    2015-01-01

    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.

  20. Ab initio calculation of intermolecular potentials for dimer Cl_2-Cl_2 and prediction of second virial coefficients

    International Nuclear Information System (INIS)

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

    2015-01-01

    The results presented in this paper are the ab initio intermolecular potentials and the second virial coefficient, B_2 (T) of the dimer Cl_2-Cl_2. These ab initio potentials were proposed by the quantum chemical calculations at high level of theory CCSD(T) with basis sets of Dunning valence correlation-consistent aug-cc-pVmZ (m = 2, 3); these results were extrapolated to complete basis set limit aug-cc-pV23Z. The ab initio energies of complete basis set limit aug-cc-pV23Z resulted from the exponential extrapolation were used to construct the 5-site pair potential functions. The second virial coefficients for this dimer were predicted from those with four-dimensional integration. The second virial coefficients were also corrected to first-order quantum effects. The results turn out to be in good agreement with experimental data, if available, or with those from empirical correlation. The quality of ab initio 5-site potentials proved the reliability for prediction of molecular thermodynamic properties. (author)

  1. Room temperature ionic liquids: A simple model. Effect of chain length and size of intermolecular potential on critical temperature.

    Science.gov (United States)

    Chapela, Gustavo A; Guzmán, Orlando; Díaz-Herrera, Enrique; del Río, Fernando

    2015-04-21

    A model of a room temperature ionic liquid can be represented as an ion attached to an aliphatic chain mixed with a counter ion. The simple model used in this work is based on a short rigid tangent square well chain with an ion, represented by a hard sphere interacting with a Yukawa potential at the head of the chain, mixed with a counter ion represented as well by a hard sphere interacting with a Yukawa potential of the opposite sign. The length of the chain and the depth of the intermolecular forces are investigated in order to understand which of these factors are responsible for the lowering of the critical temperature. It is the large difference between the ionic and the dispersion potentials which explains this lowering of the critical temperature. Calculation of liquid-vapor equilibrium orthobaric curves is used to estimate the critical points of the model. Vapor pressures are used to obtain an estimate of the triple point of the different models in order to calculate the span of temperatures where they remain a liquid. Surface tensions and interfacial thicknesses are also reported.

  2. 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.

  3. 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.

  4. 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.

  5. Ruthenium(II)-Catalyzed C-H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate-Controlled Synthesis of Indoles and 3H-Indoles.

    Science.gov (United States)

    Li, Yunyun; Qi, Zisong; Wang, He; Yang, Xifa; Li, Xingwei

    2016-09-19

    Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor-acceptor diazo compounds were developed that afforded NH indoles and 3H-indoles under ruthenium catalysis. The coupling of α-diazoketoesters afforded NH indoles by cleavage of the C(N2 )-C(acyl) bond whereas α-diazomalonates gave 3H-indoles by C-N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium-catalyzed C-H activation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Controlled Self-Assembly of Low-Dimensional Alq3 Nanostructures from 1D Nanowires to 2D Plates via Intermolecular Interactions

    Science.gov (United States)

    Gu, Jianmin; Yin, Baipeng; Fu, Shaoyan; Jin, Cuihong; Liu, Xin; Bian, Zhenpan; Li, Jianjun; Wang, Lu; Li, Xiaoyu

    2018-03-01

    Due to the intense influence of the shape and size of the photon building blocks on the limitation and guidance of optical waves, an important strategy is the fabrication of different structures. Herein, organic semiconductor tris-(8-hydroxyquinoline)aluminium (Alq3) nanostructures with controllable morphology, ranging from one-dimensional nanowires to two-dimensional plates, have been prepared through altering intermolecular interactions with employing the anti-solvent diffusion cooperate with solvent-volatilization induced self-assembly method. The morphologies of the formed nanostructures, which are closely related to the stacking modes of the molecules, can be exactly controlled by altering the polarity of anti-solvents that can influence various intermolecular interactions. The synthesis strategy reported here can potentially be extended to other functional organic nanomaterials.

  7. Decomposition of Intermolecular Interactions in the Crystal Structure of Some Diacetyl Platinum(II Complexes: Combined Hirshfeld, AIM, and NBO Analyses

    Directory of Open Access Journals (Sweden)

    Saied M. Soliman

    2016-12-01

    Full Text Available Intermolecular interactions play a vital role in crystal structures. Therefore, we conducted a topological study, using Hirshfeld surfaces and atom in molecules (AIM analysis, to decompose and analyze, respectively, the different intermolecular interactions in six hydrazone-diacetyl platinum(II complexes. Using AIM and natural bond orbital (NBO analyses, we determined the type, nature, and strength of the interactions. All the studied complexes contain C-H⋯O interactions, and the presence of bond critical points along the intermolecular paths underlines their significance. The electron densities (ρ(r at the bond critical points (0.0031–0.0156 e/a03 fall within the typical range for H-bonding interactions. Also, the positive values of the Laplacian of the electron density (∇2ρ(r revealed the depletion of electronic charge on the interatomic path, another characteristic feature of closed-shell interactions. The ratios of the absolute potential energy density to the kinetic energy density (|V(r|/G(r and ρ(r are highest for the O2⋯H15-N3 interaction in [Pt(COMe2(2-pyCMe=NNH2] (1; hence, this interaction has the highest covalent character of all the O⋯H intermolecular interactions. Interestingly, in [Pt(COMe2(H2NN=CMe-CMe=NNH2] (3, there are significant N-H⋯Pt interactions. Using the NBO method, the second-order interaction energies, E(2, of these interactions range from 3.894 to 4.061 kJ/mol. Furthermore, the hybrid Pt orbitals involved in these interactions are comprised of dxy, dxz, and s atomic orbitals.

  8. Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

    International Nuclear Information System (INIS)

    Xuelei Chu; Ohmoto, Hiroshi

    1991-01-01

    For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

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

    International Nuclear Information System (INIS)

    Almeida, Ana R.R.P.; Monte, Manuel J.S.

    2014-01-01

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

  10. Radiative transitions for the Cs2NaErCl6 elpasolite crystal. I.- Vibronic intensities for the emissions |(4115/2)Γk]≤| (4I13/2)Γl] in the Cs2NaErCl6

    International Nuclear Information System (INIS)

    Acevedo, R.; Escudero, M; Navarro, G; Meruane, T

    2002-01-01

    In this paper, we report explicit calculations for the spectral intensities of the seventy-five emissions |( 4 I 1372 )Γ k ]→ ( 4 I 15/2 )Γ l ] +v m ; m=3,4,6, where the irreducible representations labels are chosen as: (Γ k ; Γ l )=(Γ 6 ,2Γ 7 ,2Γ 8 ; Γ 6 , Γ 7 ,3Γ 8 , of the ErCl 3- 6 clusters in the Cs 2 NaErCl 6 crystal. The details of the spectrum suggest that in an energy range of about 400cm -1 , a substantial number of transitions [25 magnetic dipole (MD) and 75 vibronic electric dipole (VED) excitations] may be observed and also that a number of super positions of these transitions is most likely to occur. This experimental evidence is rather complicated to analyze and there is a need for more theoretical backup to gain understanding in both radiative and non-radiative processes in these materials. In this paper, we have taken a broader view of the intensity mechanisms associated with vibronically allowed electronic transitions and have decided to further test our current calculation models (VCF-LP) with reference to the |( 4 I 13/2 )Γ k ]→|( 4 I 15/2 )Γl]+v m , emissions for this crystal. It is interesting to realize that, although the intrinsic limitations of our models and methods to estimate spectral intensities, the final output (calculated oscillator strengths) indicate a fair and sensible agreement between our theoretical predictions and experimental data. As a further test of our vibronic intensity model, in a forthcoming paper, we will examine the rather unusual high intensity associated with the |( 4 S 3/ ) Γ l →|( 4 I 15/2 )Γ k ] emissions for this elpasolite (author)

  11. Radiative transitions for the Cs2NaErCl6 elpasolite crystal. II.- Vibronic intensities for the emissions |(4S3/2Γ8]→4I15/2Γ] in the Cs2NaErCl6

    International Nuclear Information System (INIS)

    Acevedo, R.; Escudero, M; Navarro, G; Meruane, T

    2002-01-01

    We have recently reported explicit vibronic intensity calculations for the emissions |( 4 I 15/ ) Γ k ]→|( 4 I 13/2 )Γ l ] of Er 3+ in the Cs 2 NaErCl 6 elpasolite system. The experimental evidence indicates than over an energy range of about 400cm -1 , a substantial number of transitions take place (about one hundred excitations; twenty five of them are magnetic dipole allowed whereas the remaining seventy five are vibronically allowed in character). The spectrum is very complex indeed and the superposition of various spectral features is most likely to occur and this represents a serious challenge to theoreticians. For this system, there is solid evidence which indicates that for the |( 4 S 3/2 )Γ 8 ]→|( 4 I 15/2 )Γ] transitions, where Γ=Γ 6 , Γ 7 , Γ 8 a , Γ 8 b , Γ 8 c , the most intense features of the spectrum are assigned to one photon electric-dipole vibronic excitations, involving the v 3 (stretching; τ 1u ), v 4 (bending; τ 1u ) and v 6 (bending; τ 2u ) moiety modes of the ErCl 3- 6 clusters in the crystal. It is the aim of this paper to explain on both a qualitative and a quantitative basis the rather unexpected high intensity with these type of transitions for which the static selection rule ΔJ=6 is operative. To achieve our goals, we introduce an intensity path and/or mechanism, according to the following radiative decay cascade: |( S 3/2 )Γ 8 ]→|( 4 I 11/2 )Γ']→|( 4 I 15/2 )]. It is shown that when this mechanism is adopted, then the calculated overall spectral intensity due to the three false origins (v 3 , v 4 , v 6 ) is in a fairly good agreement with experiment (author)

  12. Synthesis of new pyrrole–pyridine-based ligands using an in situ Suzuki coupling method

    Directory of Open Access Journals (Sweden)

    Matthias Böttger

    2012-07-01

    Full Text Available The compounds 6-(pyrrol-2-yl-2,2‘-bipyridine, 2-(pyrrol-2-yl-1,10-phenanthroline and 2-(2-(N-methylbenz[d,e]imidazole-6-(pyrrol-2-yl-pyridine were synthesized by using an in situ generated boronic acid for the Suzuki coupling. Crystals of the products could be grown and exhibited interesting structures by X-ray analysis, one of them showing a chain-like network with the adjacent molecules linked to each other via intermolecular N–H…N hydrogen bonds.

  13. Coupling effects in heterostructures of pentacene and perfluorinated pentacene studied by optical spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Broch, Katharina; Heinemeyer, Ute; Hinderhofer, Alexander; Gerlach, Alexander; Schreiber, Frank [Institut fuer Angewandte Physik, Tuebingen (Germany); Anger, Falk [Institut fuer Angewandte Physik, Tuebingen (Germany); MATGAS 2000 AIE, Campus de la UAB, Bellaterra (Spain); Osso, Oriol [MATGAS 2000 AIE, Campus de la UAB, Bellaterra (Spain); Scholz, Reinhard [Walter Schottky Institut, Technische Universitaet Muenchen, Garching (Germany)

    2010-07-01

    Heterostructures of organic semiconductors gain increasing interest in the last years because of their potential applications in organic electronics. To optimize those devices the understanding of the intermolecular coupling is crucial. Therefore, we investigate the optical absorption spectra of heterostructures and possible differences to the spectra of their single components. The combination of pentacene (PEN) with perfluorinated pentacene (PFP) is promising due to their similar geometric structure which can give rise to coevaporated films with a significant level of intermixing and accordingly an efficient intermolecular coupling. Indeed, performing in-situ-measurements with differential reflectance spectroscopy and spectroscopic ellipsometry we find features in the absorption spectra of mixed films that cannot be explained by a linear combination of the single film spectra. In the energy range between 1.4 eV and 2.4 eV spectra of PFP and PEN single and coevaporated films with different mixing ratios are compared and possible theoretical scenarios for coupling effects are discussed.

  14. Microassembly by intermolecular forces

    International Nuclear Information System (INIS)

    Henderson, S.J.; White, J.W.

    1988-01-01

    The value of neutron and X-ray small-angle scattering for studying self assembly of molecular-sized units into interesting chemical and electrical structures is illustrated with three different types of system. The amphiphilic nature of a polyacetylene-polyisoprene [(CH) x PI] AB block copolymer and some of the structure arising from this are seen in neutron scattering from (CD) x PI solids and solutions. The action of template molecules in zeolite synthesis is discussed and template action of the tetrapropylammonium ion at room temperature in soluble silicate gels demonstrated. Finally, very large interplatelet spacings in clay sols are recorded using small-angle X-ray scattering and the swelling behaviour of these systems is characterized. Their usefulness for pillared clay synthesis is discussed. (orig.)

  15. Path coupling and aggregate path coupling

    CERN Document Server

    Kovchegov, Yevgeniy

    2018-01-01

    This book describes and characterizes an extension to the classical path coupling method applied to statistical mechanical models, referred to as aggregate path coupling. In conjunction with large deviations estimates, the aggregate path coupling method is used to prove rapid mixing of Glauber dynamics for a large class of statistical mechanical models, including models that exhibit discontinuous phase transitions which have traditionally been more difficult to analyze rigorously. The book shows how the parameter regions for rapid mixing for several classes of statistical mechanical models are derived using the aggregate path coupling method.

  16. Conformations and Intermolecular Interactions in Cellulose/Silk Fibroin Blend Films: A Solid-State NMR Perspective.

    Science.gov (United States)

    Tian, Donglin; Li, Tao; Zhang, Rongchun; Wu, Qiang; Chen, Tiehong; Sun, Pingchuan; Ramamoorthy, Ayyalusamy

    2017-06-29

    Fabricating materials with excellent mechanical performance from the natural renewable and degradable biopolymers has drawn significant attention in recent decades due to the environmental concerns and energy crisis. As two of the most promising substitutes of synthetic polymers, silk fibroin (SF), and cellulose, have been widely used in the field of textile, biomedicine, biotechnology, etc. Particularly, the cellulose/SF blend film exhibits better strength and toughness than that of regenerated cellulose film. Herein, this study is aimed to understand the molecular origin of the enhanced mechanical properties for the cellulose/SF blend film, using solid-state NMR as a main tool to investigate the conformational changes, intermolecular interactions between cellulose and SF and the water organization. It is found that the content of the β-sheet structure is increased in the cellulose/SF blend film with respect to the regenerated SF film, accompanied by the reduction of the content of random coil structures. In addition, the strong hydrogen bonding interaction between the SF and cellulose is clearly elucidated by the two-dimensional (2D) 1 H- 13 C heteronuclear correlation (HETCOR) NMR experiments, demonstrating that the SF and cellulose are miscible at the molecular level. Moreover, it is also found that the -NH groups of SF prefer to form hydrogen bonds with the hydroxyl groups bonded to carbons C2 and C3 of cellulose, while the hydroxyl groups bonded to carbon C6 and the ether oxygen are less favorable for hydrogen bonding interactions with the -NH groups of SF. Interestingly, bound water is found to be present in the air-dried cellulose/SF blend film, which is predominantly associated with the cellulose backbones as determined by 2D 1 H- 13 C wide-line-separation (WISE) experiments with spin diffusion. This clearly reveals the presence of nanoheterogeneity in the cellulose/SF blend film, although cellulose and SF are miscible at a molecular level. Without doubt

  17. Nitroxide stable radicals interacting as Lewis bases in hydrogen bonds: A search in the Cambridge structural data base for intermolecular contacts

    Science.gov (United States)

    Alkorta, Ibon; Elguero, José; Elguero, Eric

    2017-11-01

    1125 X-ray structures of nitroxide free radicals presenting intermolecular hydrogen bonds have been reported in the Cambridge Structural Database. We will report in this paper a qualitative and quantitative analysis of these bonds. The observation in some plots of an excluded region was statistically analyzed using convex hull and kernel smooting methodologies. A theoretical study at the MP2 level with different basis has been carried out indicating that the nitronyl nitroxide radicals (five electrons) lie just in between nitroso compounds (four electrons) and amine N-oxides (six electrons) as far as hydrogen-bond basicity is concerned.

  18. Excitonic Coupling in Linear and Trefoil Trimer Perylenediimide Molecules Probed by Single-Molecule Spectroscopy

    KAUST Repository

    Yoo, Hyejin

    2012-10-25

    Perylenediimide (PDI) molecules are promising building blocks for photophysical studies of electronic interactions within multichromophore arrays. Such PDI arrays are important materials for fabrication of molecular nanodevices such as organic light-emitting diodes, organic semiconductors, and biosensors because of their high photostability, chemical and physical inertness, electron affinity, and high tinctorial strength over the entire visible spectrum. In this work, PDIs have been organized into linear (L3) and trefoil (T3) trimer molecules and investigated by single-molecule fluorescence microscopy to probe the relationship between molecular structures and interchromophoric electronic interactions. We found a broad distribution of coupling strengths in both L3 and T3 and hence strong/weak coupling between PDI units by monitoring spectral peak shifts in single-molecule fluorescence spectra upon sequential photobleaching of each constituent chromophore. In addition, we used a wide-field defocused imaging technique to resolve heterogeneities in molecular structures of L3 and T3 embedded in a PMMA polymer matrix. A systematic comparison between the two sets of experimental results allowed us to infer the correlation between intermolecular interactions and molecular structures. Our results show control of the PDI intermolecular interactions using suitable multichromophoric structures. © 2012 American Chemical Society.

  19. Excitonic Coupling in Linear and Trefoil Trimer Perylenediimide Molecules Probed by Single-Molecule Spectroscopy

    KAUST Repository

    Yoo, Hyejin; Furumaki, Shu; Yang, Jaesung; Lee, Ji-Eun; Chung, Heejae; Oba, Tatsuya; Kobayashi, Hiroyuki; Rybtchinski, Boris; Wilson, Thea M.; Wasielewski, Michael R.; Vacha, Martin; Kim, Dongho

    2012-01-01

    Perylenediimide (PDI) molecules are promising building blocks for photophysical studies of electronic interactions within multichromophore arrays. Such PDI arrays are important materials for fabrication of molecular nanodevices such as organic light-emitting diodes, organic semiconductors, and biosensors because of their high photostability, chemical and physical inertness, electron affinity, and high tinctorial strength over the entire visible spectrum. In this work, PDIs have been organized into linear (L3) and trefoil (T3) trimer molecules and investigated by single-molecule fluorescence microscopy to probe the relationship between molecular structures and interchromophoric electronic interactions. We found a broad distribution of coupling strengths in both L3 and T3 and hence strong/weak coupling between PDI units by monitoring spectral peak shifts in single-molecule fluorescence spectra upon sequential photobleaching of each constituent chromophore. In addition, we used a wide-field defocused imaging technique to resolve heterogeneities in molecular structures of L3 and T3 embedded in a PMMA polymer matrix. A systematic comparison between the two sets of experimental results allowed us to infer the correlation between intermolecular interactions and molecular structures. Our results show control of the PDI intermolecular interactions using suitable multichromophoric structures. © 2012 American Chemical Society.

  20. Electromagnetic clutches and couplings

    CERN Document Server

    Vorob'Yeva, T M; Fry, D W; Higinbotham, W

    2013-01-01

    Electromagnetic Clutches and Couplings contains a detailed description of U.S.S.R. electromagnetic friction clutches, magnetic couplings, and magnetic particle couplings. This book is divided into four chapters. The first chapter discusses the design and construction of magnetic (solenoid-operated) couplings, which are very quick-acting devices and used in low power high-speed servo-systems. Chapter 2 describes the possible fields of application, design, construction, and utilization of magnetic particle couplings. The aspects of construction, design, and utilization of induction clutches (sli

  1. Vibronic excitation in atom molecule collisions

    International Nuclear Information System (INIS)

    Kleyn, A.W.

    1980-01-01

    The molecular beam machine used for the experiments is described. Three setups are discussed: one to measure total cross sections for negative ion formation in Na, K, Cs + O 2 collisions (3-6000 eV); another to measure differential cross sections for neutral scattering and positive ion formation in K, Cs + O 2 and K + Br 2 collisions (20 - 150 eV); and a third to measure energy-loss spectra for neutral K scattered at a certain angle after a collision with O 2 or Br 2 (20 - 150 eV). (Auth.)

  2. Synthesis and studies on structural, optical and nonlinear optical properties of novel organic inter-molecular compounds: 4-chloro-3-nitroaniline-3-hydroxy benzaldehyde and urea-4-dimethylaminopyridine

    Science.gov (United States)

    Pandey, Priyanka; Rai, R. N.

    2018-05-01

    Two novel organic inter-molecular compounds (IMCs), (3-(4-chloro-3-nitrophenylimino) methyl) phenol) (CNMP) and urea ̶ 4-dimethylaminopyridine complex (UDMAP), have been synthesized by solid state reaction. These two IMCs were identified by phase diagram study of CNA-HB and U-DMAP systems. The single crystals of newly obtained IMCs were grown by slow solvent evaporation technique at room temperature. Both the IMCs were further studied for their thermal, spectral, single crystal XRD for their atomic packing in molecule, crystallinity, optical and nonlinear optical behaviour. In both the cases, melting point of inter-molecular compounds was found to be higher than that of their parent components, CNMP was found to be thermally stable up to 158 °C while UDMAP was stable up to 144 °C, which indicate their extra stability than their parents. The single crystal XRD studies confirmed that CNMP has crystallized in orthorhombic unit cell with non-centrosymmetric space group P212121 while UDMAP has crystallized in monoclinic unit cell with centrosymmetric space group C2/c. The absorption spectrum of CNMP was found to be in between the absorption of parents, while broadening of peak and red shift was observed in UDMAP as compared to the parents. Second order nonlinear optical property of CNMP and UDMAP was studied using Kurtz Perry powder technique and intense green light emission was observed with CNMP on excitation with 1064 nm of Nd:YAG laser while no emission was observed with UDMAP.

  3. Transport properties in mixtures involving carbon dioxide at low and moderate density: test of several intermolecular potential energies and comparison with experiment

    Science.gov (United States)

    Moghadasi, Jalil; Yousefi, Fakhri; Papari, Mohammad Mehdi; Faghihi, Mohammad Ali; Mohsenipour, Ali Asghar

    2009-09-01

    It is the purpose of this paper to extract unlike intermolecular potential energies of five carbon dioxide-based binary gas mixtures including CO2-He, CO2-Ne, CO2-Ar, CO2-Kr, and CO2-Xe from viscosity data and compare the calculated potentials with other models potential energy reported in literature. Then, dilute transport properties consisting of viscosity, diffusion coefficient, thermal diffusion factor, and thermal conductivity of aforementioned mixtures are calculated from the calculated potential energies and compared with literature data. Rather accurate correlations for the viscosity coefficient of afore-cited mixtures embracing the temperature range 200 K < T < 3273.15 K is reproduced from the present unlike intermolecular potentials energy. Our estimated accuracies for the viscosity are to within ±2%. In addition, the calculated potential energies are used to present smooth correlations for other transport properties. The accuracies of the binary diffusion coefficients are of the order of ±3%. Finally, the unlike interaction energy and the calculated low density viscosity have been employed to calculate high density viscosities using Vesovic-Wakeham method.

  4. Transport properties in mixtures involving carbon dioxide at low and moderate density: test of several intermolecular potential energies and comparison with experiment

    Energy Technology Data Exchange (ETDEWEB)

    Moghadasi, Jalil; Yousefi, Fakhri [Shiraz University, Department of Chemistry, Shiraz (Iran); Papari, Mohammad Mehdi; Faghihi, Mohammad Ali [Shiraz University of Technology, Department of Chemistry, Shiraz (Iran); Mohsenipour, Ali Asghar [University of Waterloo, Department of Chemical Engineering, Waterloo (Canada)

    2009-09-15

    It is the purpose of this paper to extract unlike intermolecular potential energies of five carbon dioxide-based binary gas mixtures including CO{sub 2}-He, CO{sub 2}-Ne, CO{sub 2}-Ar, CO{sub 2}-Kr, and CO{sub 2}-Xe from viscosity data and compare the calculated potentials with other models potential energy reported in literature. Then, dilute transport properties consisting of viscosity, diffusion coefficient, thermal diffusion factor, and thermal conductivity of aforementioned mixtures are calculated from the calculated potential energies and compared with literature data. Rather accurate correlations for the viscosity coefficient of afore-cited mixtures embracing the temperature range 200 Kintermolecular potentials energy. Our estimated accuracies for the viscosity are to within {+-}2%. In addition, the calculated potential energies are used to present smooth correlations for other transport properties. The accuracies of the binary diffusion coefficients are of the order of {+-}3%. Finally, the unlike interaction energy and the calculated low density viscosity have been employed to calculate high density viscosities using Vesovic-Wakeham method. (orig.)

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

    Directory of Open Access Journals (Sweden)

    Takashi Yamamoto

    2012-07-01

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

  6. Unambiguous Determination of Intermolecular Hydrogen Bond of NMR Structure by Molecular Dynamics Refinement Using All-Atom Force Field and Implicit Solvent Model

    International Nuclear Information System (INIS)

    Jee, Jun Goo

    2010-01-01

    It has been shown that AMD refinement is very useful for defining an intermolecular hydrogen bond in NMR structure calculation. The refined structure also provides a clue for explaining the pH dependence in Ub and UIM complexes. As reported by Choi et al., serine-mediated hydrogen bonds are the third most populated hydrogen bonds found in protein-protein intermolecular interactions, after the backbone-backbone and backbone-aspartate ones. The abundance imposes the requirement of an method to determine the interface of protein-protein complexes. The precise geometry is particularly important in the complex structures between Ub and UBDs. Ub recognizes various targets with the same surface, where both hydrophobic and hydrophobic interactions are involved. Hence, the details of the hydrophilic interactions are necessary to find the common binding modes. The structure determination of a biomolecule by NMR depends heavily on the distance restraints derived by the NOE cross peaks that are observed between two protons within 6 A through space. Therefore, the existence of the NOE peaks and their correct assignments to two corresponding protons are essential for an accurate and precise structure determination. Recent developments of NOE assignment and calculation algorithms have enabled the determination of protein 3D structures without any manual interpretation, provided chemical shifts are assigned in most atoms and sufficient NOE peaks exist. Along with these advances, the necessity of determining complicated structures such as complexes is increasing

  7. Intra- versus Intermolecular Hydrogen Bonding: Solvent-Dependent Conformational Preferences of a Common Supramolecular Binding Motif from 1 H NMR and Vibrational Circular Dichroism Spectra.

    Science.gov (United States)

    Demarque, Daniel P; Merten, Christian

    2017-12-19

    When predicting binding properties of small molecules or larger supramolecular aggregates, intra- and intermolecular hydrogen bonds are often considered the most important factor. Spectroscopic techniques such as 1 H NMR spectroscopy are typically utilized to characterize such binding events, but interpretation is often qualitative and follows chemical intuition. In this study, we compare the effects of intramolecular hydrogen bonding and solvation on two chiral 2,6-pyridinediyl-dialkylamides. In comparison with 1 H NMR spectroscopy, vibrational circular dichroism (VCD) spectroscopy proved to be more sensitive to conformational changes. In fact, the change of the solvent from CDCl 3 to [D 6 ]DMSO generates mirror-image VCD spectra for the same enantiomer. Here, the common sense that the sterically less hindered group is more prone to solvation proved to be wrong according predicted VCD spectra, which clearly show that both asymmetric amide hydrogens are equally likely to be solvated, but never simultaneously. The competition between intra- and intermolecular hydrogen bonding and their importance for a correct prediction of spectral properties are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Solid state synthesis, structural, physicochemical and optical properties of an inter-molecular compound: 2-hydroxy-1, 2-diphenylethanone-4-nitro-o-phenylenediamine system

    Science.gov (United States)

    Rai, U. S.; Singh, Manjeet; Rai, R. N.

    2017-09-01

    The phase diagram of 2-hydroxy-1, 2-diphenylethanone (HDPE)-4-nitro-o-phenylenediamine (NOPDA) system, determined by the thaw-melt method, gives two eutectics E1 (m p = 66.0 °C) and E2 (m p = 155.0 °C) with 0.30 and 0.55 mol fractions of NOPDA, respectively, and an 1:1 inter-molecular compound (IMC) (m p 162.0 °C). This IMC was synthesized by adopting the green synthetic method of solid state reaction. While its formation and structure were confirmed by the X-ray diffraction and spectroscopic methods, the ORTEP view gives mode of crystal packing, C‒H…O, C‒H…N, π-π stacking and the inter-molecular hydrogen bonding in the compound. The single crystal of the IMC shows 53% transmission and emits significantly higher dual fluorescence, and the band gap was computed to be 3.04 eV. The values of solubility of the IMC, measured in the temperature range 304-322 K, satisfy the mole fraction (X) and temperature equation: Xeq= 5.1324 × 10-7 e 0.01356T.

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

    International Nuclear Information System (INIS)

    Phadke, Sushil; Shrivastava, Bhakt Darshan; Ujle, S K; Mishra, Ashutosh; Dagaonkar, N

    2014-01-01

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

  10. Crystal structures of 4-chloropyridine-2-carbonitrile and 6-chloropyridine-2-carbonitrile exhibit different intermolecular π-stacking, C—H...Nnitrile and C—H...Npyridine interactions

    Directory of Open Access Journals (Sweden)

    Matthew J. Montgomery

    2015-07-01

    Full Text Available The two title compounds are isomers of C6H3ClN2 containing a pyridine ring, a nitrile group, and a chloro substituent. The molecules of each compound pack together in the solid state with offset face-to-face π-stacking, and intermolecular C—H...Nnitrile and C—H...Npyridine interactions. 4-Chloropyridine-2-carbonitrile, (I, exhibits pairwise centrosymmetric head-to-head C—H...Nnitrile and C—H...Npyridine interactions, forming one-dimensional chains, which are π-stacked in an offset face-to-face fashion. The intermolecular packing of the isomeric 6-chloropyridine-2-carbonitrile, (II, which differs only in the position of the chloro substituent on the pyridine ring, exhibits head-to-tail C—H...Nnitrile and C—H...Npyridine interactions, forming two-dimensional sheets which are π-stacked in an offset face-to-face fashion. In contrast to (I, the offset face-to-face π-stacking in (II is formed between molecules with alternating orientations of the chloro and nitrile substituents.

  11. Geminal-spanning orbitals make explicitly correlated reduced-scaling coupled-cluster methods robust, yet simple

    Science.gov (United States)

    Pavošević, Fabijan; Neese, Frank; Valeev, Edward F.

    2014-08-01

    We present a production implementation of reduced-scaling explicitly correlated (F12) coupled-cluster singles and doubles (CCSD) method based on pair-natural orbitals (PNOs). A key feature is the reformulation of the explicitly correlated terms using geminal-spanning orbitals that greatly reduce the truncation errors of the F12 contribution. For the standard S66 benchmark of weak intermolecular interactions, the cc-pVDZ-F12 PNO CCSD F12 interaction energies reproduce the complete basis set CCSD limit with mean absolute error cost compared to the conventional CCSD F12.

  12. Effect of intermolecular cohesion on coal liquefaction. 3. Reactivity of oxygen methylated coal; Sekitan teibunshika hanno ni okeru bunshikan gyoshuryoku no koka. 3. O-methyl ka tan no hanno tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Sasaki, M.; Nagaishi, H.; Yoshida, T. [Hokkaido National Industrial Research Institute, Sapporo (Japan)

    1996-10-28

    The reactivity of oxygen methylated coal was studied to control hydrogen bond in bituminous coal liquefaction and intermolecular cohesion such as van der Waals force. In experiment, crushed and dried Illinois coal of 100mesh or less was used as specimen, and oxygen methylated coal was prepared by Liotta`s method using tetrabutylammonium halide. Coal liquefaction was conducted in an electromagnetic agitation autoclave using tetralin solvent under initial hydrogen pressure of 100kg/cm{sup 2} while heating. The molecular weight distribution of the products obtained was measured by gel permeation chromatography (GPC) analysis. The experimental results are as follows. The effect of intermolecular cohesion in bituminous coal on the reactivity is mainly derived from decomposing reaction from preasphaltene to oil. Yields of oil fraction by methylation increase corresponding to release of intermolecular cohesion. Since the thermal release is promoted with temperature rise, the difference in yield due to different treatments decreases. 5 refs., 3 figs., 1 tab.

  13. Conversation, coupling and complexity

    DEFF Research Database (Denmark)

    Fusaroli, Riccardo; Abney, Drew; Bahrami, Bahador

    We investigate the linguistic co-construction of interpersonal synergies. By applying a measure of coupling between complex systems to an experimentally elicited corpus of joint decision dialogues, we show that interlocutors’ linguistic behavior displays increasing signature of multi-scale coupling......, known as complexity matching, over the course of interaction. Furthermore, we show that stronger coupling corresponds with more effective interaction, as measured by collective task performance....

  14. Coupling Integrable Couplings of an Equation Hierarchy

    International Nuclear Information System (INIS)

    Wang Hui; Xia Tie-Cheng

    2013-01-01

    Based on a kind of Lie algebra G proposed by Zhang, one isospectral problem is designed. Under the framework of zero curvature equation, a new kind of integrable coupling of an equation hierarchy is generated using the methods proposed by Ma and Gao. With the help of variational identity, we get the Hamiltonian structure of the hierarchy. (general)

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

    Directory of Open Access Journals (Sweden)

    Takayuki Odahara

    2016-06-01

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

  16. Ab initio study of the CO-N2 complex: a new highly accurate intermolecular potential energy surface and rovibrational spectrum

    DEFF Research Database (Denmark)

    Cybulski, Hubert; Henriksen, Christian; Dawes, Richard

    2018-01-01

    A new, highly accurate ab initio ground-state intermolecular potential-energy surface (IPES) for the CO-N2 complex is presented. Thousands of interaction energies calculated with the CCSD(T) method and Dunning's aug-cc-pVQZ basis set extended with midbond functions were fitted to an analytical...... function. The global minimum of the potential is characterized by an almost T-shaped structure and has an energy of -118.2 cm-1. The symmetry-adapted Lanczos algorithm was used to compute rovibrational energies (up to J = 20) on the new IPES. The RMSE with respect to experiment was found to be on the order...... of 0.038 cm-1 which confirms the very high accuracy of the potential. This level of agreement is among the best reported in the literature for weakly bound systems and considerably improves on those of previously published potentials....

  17. Translation-coupling systems

    Science.gov (United States)

    Pfleger, Brian; Mendez-Perez, Daniel

    2013-11-05

    Disclosed are systems and methods for coupling translation of a target gene to a detectable response gene. A version of the invention includes a translation-coupling cassette. The translation-coupling cassette includes a target gene, a response gene, a response-gene translation control element, and a secondary structure-forming sequence that reversibly forms a secondary structure masking the response-gene translation control element. Masking of the response-gene translation control element inhibits translation of the response gene. Full translation of the target gene results in unfolding of the secondary structure and consequent translation of the response gene. Translation of the target gene is determined by detecting presence of the response-gene protein product. The invention further includes RNA transcripts of the translation-coupling cassettes, vectors comprising the translation-coupling cassettes, hosts comprising the translation-coupling cassettes, methods of using the translation-coupling cassettes, and gene products produced with the translation-coupling cassettes.

  18. Ligand field and intermolecular interactions tuning the magnetic properties of spin-crossover Fe(II) polymer with 4,4′-bipyridine

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Yang-Hui; Liu, Qing-Ling; Yang, Li-Jing; Ling, Yang; Wang, Wei; Sun, Bai-Wang, E-mail: chmsunbw@seu.edu.cn

    2015-02-15

    A new spin crossover coordination polymer (SCO-CPs) of Fe(II)-4,4′-bipyridine (4,4′-bipy) family: (Fe(4,4′-bipy){sub 2}(H{sub 2}O){sub 2})·(4,4′-bipy)· 8(H{sub 2}O)·2(ClO{sub 4}) (3), which displays half spin transitions between 100 and 300 K, has been synthesized and structurally characterized. Compound 3 featured with two-dimensional (2-D) grids connected by hydrogen bonds and π…π packing between one-dimensional (1-D) chains, the 2-D grids expand to three-dimensional (3-D) architecture supported by a “S-shaped holder” involving lattice 4-4′-bipy, water molecules and perchlorate anion. We compared 3 with the other two analogous complexes: ((Fe(4,4′-bipy) (H{sub 2}O){sub 2} (NCS){sub 2})·4,4′-bipy, 1 and (Fe(4,4′-bipy){sub 2}(NCS){sub 2})·mSolv, 2) through Hirshfeld surfaces analysis, which revealed that the low ligand field strength (NCS{sup −}) and lone-pair…H contacts contribute to the stabilization of HS (high-spin) state of the Fe(II) ion, while the high ligand field strength (4,4′-bipy) and strong intermolecular contacts (hydrogen bonds and π…π packing interactions) make for the LS (low-spin) state. - Highlights: ●A new member of Fe(||)-4,4′-bipy family has been prepared. ●It displays half spin transitions tuned by ligand field and intermolecular interactions. ●We have made a detailed comparison of this new member with two other analogous complexes.

  19. Spectroscopic study on the intermolecular interaction of SO{sub 2} absorption in poly-ethylene glycol+H{sub 2}O systems

    Energy Technology Data Exchange (ETDEWEB)

    He, Zhiqiang; Liu, Jinrong; Zhang, Jianbin; Zhang, Na [Inner Mongolia University of Technology, Huhhot (China)

    2014-03-15

    Poly-Ethylene Glycol (PEG) 300+H{sub 2}O solutions (PEGWs) has been used as a promising medium for the absorption of SO{sub 2}. We investigated the UV, FTIR, {sup 1}H-NMR, and fluorescence spectra in the absorption processes of SO{sub 2} in PEGWs to present an important absorption mechanism. Based on the spectral results, the possibility of intermolecular hydrogen bond formation by hydroxyl oxygen atom in the PEG molecule with hydrogen atom in H{sub 2}O and S…O interaction formation by the oxygen atoms in PEG with the sulfur atom in SO{sub 2} are discussed. This shows that the spectral changes may be due to the formation of -CH{sub 2}CH{sub 2}O(H)…HOH… and -CH{sub 2}-CH{sub 2}-O(CH{sub 2}-CH{sub 2}-)…HOH… in PEGWs and the formation of -CH{sub 2}CH{sub 2}OH…OSO…, and intermolecular S…O interaction between PEG and SO{sub 2} as the formation of -CH{sub 2}CH{sub 2}OCH{sub 2}CH{sub 2}O(H)…(O)S(O)… and -CH{sub 2}-CH{sub 2}-O(CH{sub 2}-CH{sub 2}-) …(O)S(O)…. The existence of these bonds benefits the absorption and desorption processes of SO{sub 2} in PEGWs.

  20. Insight into the intermolecular recognition mechanism between Keap1 and IKKβ combining homology modelling, protein-protein docking, molecular dynamics simulations and virtual alanine mutation.

    Directory of Open Access Journals (Sweden)

    Zheng-Yu Jiang

    Full Text Available Degradation of certain proteins through the ubiquitin-proteasome pathway is a common strategy taken by the key modulators responsible for stress responses. Kelch-like ECH-associated protein-1(Keap1, a substrate adaptor component of the Cullin3 (Cul3-based ubiquitin E3 ligase complex, mediates the ubiquitination of two key modulators, NF-E2-related factor 2 (Nrf2 and IκB kinase β (IKKβ, which are involved in the redox control of gene transcription. However, compared to the Keap1-Nrf2 protein-protein interaction (PPI, the intermolecular recognition mechanism of Keap1 and IKKβ has been poorly investigated. In order to explore the binding pattern between Keap1 and IKKβ, the PPI model of Keap1 and IKKβ was investigated. The structure of human IKKβ was constructed by means of the homology modeling method and using reported crystal structure of Xenopus laevis IKKβ as the template. A protein-protein docking method was applied to develop the Keap1-IKKβ complex model. After the refinement and visual analysis of docked proteins, the chosen pose was further optimized through molecular dynamics simulations. The resulting structure was utilized to conduct the virtual alanine mutation for the exploration of hot-spots significant for the intermolecular interaction. Overall, our results provided structural insights into the PPI model of Keap1-IKKβ and suggest that the substrate specificity of Keap1 depend on the interaction with the key tyrosines, namely Tyr525, Tyr574 and Tyr334. The study presented in the current project may be useful to design molecules that selectively modulate Keap1. The selective recognition mechanism of Keap1 with IKKβ or Nrf2 will be helpful to further know the crosstalk between NF-κB and Nrf2 signaling.

  1. CP/MAS 13C NMR characterization of the isomeric states and intermolecular packing in tris(8-hydroxyquinoline) aluminum(III) (Alq3).

    Science.gov (United States)

    Kaji, Hironori; Kusaka, Yasunari; Onoyama, Goro; Horii, Fumitaka

    2006-04-05

    The isomeric states and intermolecular packing of tris(8-hydroxyquinoline) aluminum(III) (Alq(3)) in the alpha-, gamma-, and delta-crystalline forms and in the amorphous state, which are important for understanding the light-emitting and electron-transport properties, have been analyzed by CP/MAS (13)C NMR. This simple NMR experiment shows that the isomeric state of alpha- and amorphous Alq(3) is meridional, whereas that of gamma- and delta-Alq(3) is facial. In the amorphous Alq(3), the inclusion of facial isomers has been under debate. Our experiments show that meridional isomers are dominant in the amorphous Alq(3), although the existence of facial isomers cannot be completely denied. The local structure of amorphous Alq(3) is similar to that of alpha-Alq(3) and is significantly different from those of gamma- and delta-Alq(3). Among these Alq(3) samples, the effect of intermolecular interaction is not found only for gamma-Alq(3). This finding can explain the good solvent solubility of gamma-Alq(3), compared with the other crystalline forms. It is also shown that the structures are locally disordered not only for amorphous Alq(3) but also for alpha-Alq(3), although clear X-ray diffraction peaks are observed for alpha-Alq(3). In contrast, the local structures of gamma- and delta-Alq(3) are well defined. A clear relation is found between the spectral patterns of CP/MAS (13)C NMR and the fluorescence wavelengths; the samples, which consist of facial isomers, show blue-shifted fluorescence compared with those of meridionals.

  2. Infrared, diode laser spectroscopy of the Ar--N2O complex: Observation of the intermolecular bending mode in combination with the highest frequency intramolecular stretching mode

    International Nuclear Information System (INIS)

    Hu, T.A.; Chappell, E.L.; Sharpe, S.W.

    1993-01-01

    Rotationally resolved vibrational spectra consisting of a-type transitions have been observed for the low-frequency, intermolecular bending mode in combination with the highest frequency, intramolecular stretching mode of Ar--N 2 O. Analysis of the spectral data places the origin of the combination band at 2256.1 cm -1 while the origin of the intramolecular stretching fundamental is at 2223.9 cm -1 . The difference between these two origins is approximately 32.2 cm -1 and agrees well with our calculated frequency of 31.5 cm -1 for the intermolecular bending mode, which was obtained by analysis of the centrifugal distortion constants. In addition, argon--nitrous oxide exhibits an anomalously large inertial defect of 10.96 amu A 2 in the combination state. This indicates a breakdown in the assumption of separation between vibration and rotation. While much of the inertial defect in the ground state can be accounted for by including Coriolis interactions, that occurring in the combination state is only partially accounted for by a similar analysis. Small, but significant changes, are observed in both the radial and angular parameters for Ar--N 2 O when going from the ground to the combination state, indicating large amplitude motion. The combination band is approximately 200 times less intense than the high-frequency, stretching fundamental of Ar--N 2 O. In addition, over 400 new rovibrational transitions are assigned to the previously observed 1 0 1 intramolecular stretching fundamental of the complex, and the subsequent rotational analysis is found to be in close agreement with earlier studies. Data were taken on a newly built, rapid-scan, diode laser spectrometer that incorporates a 12 cmx200 μm pulsed slit-expansion nozzle

  3. Plastics pipe couplings

    International Nuclear Information System (INIS)

    Glover, J.B.

    1980-07-01

    A method is described of making a pipe coupling of the type comprising a plastics socket and a resilient annular sealing member secured in the mouth thereof, in which the material of at least one component of the coupling is subjected to irradiation with high energy radiation whereby the material is caused to undergo cross-linking. As examples, the coupling may comprise a polyethylene or plasticised PVC socket the material of which is subjected to irradiation, and the sealing member may be moulded from a thermoplastic elastomer which is subjected to irradiation. (U.K.)

  4. Chromophore-Dependent Intramolecular Exciton-Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics.

    Science.gov (United States)

    Padula, Daniele; Lee, Myeong H; Claridge, Kirsten; Troisi, Alessandro

    2017-11-02

    In this paper, we adopt an approach suitable for monitoring the time evolution of the intramolecular contribution to the spectral density of a set of identical chromophores embedded in their respective environments. We apply the proposed method to the Fenna-Matthews-Olson (FMO) complex, with the objective to quantify the differences among site-dependent spectral densities and the impact of such differences on the exciton dynamics of the system. Our approach takes advantage of the vertical gradient approximation to reduce the computational demands of the normal modes analysis. We show that the region of the spectral density that is believed to strongly influence the exciton dynamics changes significantly in the timescale of tens of nanoseconds. We then studied the impact of the intramolecular vibrations on the exciton dynamics by considering a model of FMO in a vibronic basis and neglecting the interaction with the environment to isolate the role of the intramolecular exciton-vibration coupling. In agreement with the assumptions in the literature, we demonstrate that high frequency modes at energy much larger than the excitonic energy splitting have negligible influence on exciton dynamics despite the large exciton-vibration coupling. We also find that the impact of including the site-dependent spectral densities on exciton dynamics is not very significant, indicating that it may be acceptable to apply the same spectral density on all sites. However, care needs to be taken for the description of the exciton-vibrational coupling in the low frequency part of intramolecular modes because exciton dynamics is more susceptible to low frequency modes despite their small Huang-Rhys factors.

  5. Coupling in the Tevatron

    International Nuclear Information System (INIS)

    Gelfand, N.M.

    1994-12-01

    The performance of the Fermilab Tevatron Collider at the commencement of run Ib was far below expectations. After a frustrating period of several months, a low-β quad downstream of the interaction point at B0 was found to be rolled. This rolled quadrupole coupled the horizontal and vertical motion of the Tevatron beams. It also made matching the beam from the Main Ring to the Tevatron impossible, resulting in emittance blow up on injection. The net result of the roll was a significant reduction in the Tevatron luminosity. When the roll in the quadrupole was corrected the performance of the Tevatron improved dramatically. This note will discuss the experimental data indicating the presence of coupling and subsequent calculations which show how coupling an affect the luminosity. It is not intended to exhaust a discussion of coupling, which hopefully will be understood well enough to be discussed in a subsequent note

  6. Coupled transverse motion

    International Nuclear Information System (INIS)

    Teng, L.C.

    1989-01-01

    The magnetic field in an accelerator or a storage ring is usually so designed that the horizontal (x) and the vertical (y) motions of an ion are uncoupled. However, because of imperfections in construction and alignment, some small coupling is unavoidable. In this lecture, we discuss in a general way what is known about the behaviors of coupled motions in two degrees-of-freedom. 11 refs., 6 figs

  7. Projected coupled cluster theory.

    Science.gov (United States)

    Qiu, Yiheng; Henderson, Thomas M; Zhao, Jinmo; Scuseria, Gustavo E

    2017-08-14

    Coupled cluster theory is the method of choice for weakly correlated systems. But in the strongly correlated regime, it faces a symmetry dilemma, where it either completely fails to describe the system or has to artificially break certain symmetries. On the other hand, projected Hartree-Fock theory captures the essential physics of many kinds of strong correlations via symmetry breaking and restoration. In this work, we combine and try to retain the merits of these two methods by applying symmetry projection to broken symmetry coupled cluster wave functions. The non-orthogonal nature of states resulting from the application of symmetry projection operators furnishes particle-hole excitations to all orders, thus creating an obstacle for the exact evaluation of overlaps. Here we provide a solution via a disentanglement framework theory that can be approximated rigorously and systematically. Results of projected coupled cluster theory are presented for molecules and the Hubbard model, showing that spin projection significantly improves unrestricted coupled cluster theory while restoring good quantum numbers. The energy of projected coupled cluster theory reduces to the unprojected one in the thermodynamic limit, albeit at a much slower rate than projected Hartree-Fock.

  8. Bridging the myoplasmic gap II: more recent advances in skeletal muscle excitation-contraction coupling.

    Science.gov (United States)

    Bannister, Roger A

    2016-01-01

    In skeletal muscle, excitation-contraction (EC) coupling relies on the transmission of an intermolecular signal from the voltage-sensing regions of the L-type Ca(2+) channel (Ca(V)1.1) in the plasma membrane to the channel pore of the type 1 ryanodine receptor (RyR1) nearly 10 nm away in the membrane of the sarcoplasmic reticulum (SR). Even though the roles of Ca(V)1.1 and RyR1 as voltage sensor and SR Ca(2+) release channel, respectively, have been established for nearly 25 years, the mechanism underlying communication between these two channels remains undefined. In the course of this article, I will review current viewpoints on this topic with particular emphasis on recent studies. © 2016. Published by The Company of Biologists Ltd.

  9. Tube coupling device

    Science.gov (United States)

    Myers, William N. (Inventor); Hein, Leopold A. (Inventor)

    1987-01-01

    A first annular ring of a tube coupling device has a keyed opening sized to fit around the nut region of a male coupling, and a second annular ring has a keyed opening sized to fit around the nut of a female coupling. Each ring has mating ratchet teeth and these rings are biased together, thereby engaging these teeth and preventing rotation of these rings. This in turn prevents the rotation of the male nut region with respect to the female nut. For tube-to-bulkhead locking, one facet of one ring is notched, and a pin is pressed into an opening in the bulkhead. This pin is sized to fit within one of the notches in the ring, thereby preventing rotation of this ring with respect to the bulkhead.

  10. EMP coupling to ships

    International Nuclear Information System (INIS)

    Deadrick, F.J.; Cabayan, H.S.; Kunz, K.F.; Bevensee, R.M.; Martin, L.C.; Egbert, R.W.

    1980-01-01

    Scale-model tests were conducted to establish the adequacy and limitations of model measurements as tools for predicting electromagnetic pulse (EMP) coupling voltages and currents to the critical antennas, cables, and metallic structures on ships. The scale-model predictions are compared with the results of the full-scale EMP simulation test of the Canadian ASW ship, HMCS Huron. (The EMP coupling predictions in this report were made without prior knowledge of the results of the data from the HMCS Huron tests.) This report establishes that the scale-model tests in conjunction with the data base from EMP coupling modules provides the necessary information for source model development and permits effective, low-cost study of particular system configurations. 184 figures, 9 tables

  11. Strong-coupling approximations

    International Nuclear Information System (INIS)

    Abbott, R.B.

    1984-03-01

    Standard path-integral techniques such as instanton calculations give good answers for weak-coupling problems, but become unreliable for strong-coupling. Here we consider a method of replacing the original potential by a suitably chosen harmonic oscillator potential. Physically this is motivated by the fact that potential barriers below the level of the ground-state energy of a quantum-mechanical system have little effect. Numerically, results are good, both for quantum-mechanical problems and for massive phi 4 field theory in 1 + 1 dimensions. 9 references, 6 figures

  12. Coupled moderator neutronics

    International Nuclear Information System (INIS)

    Russell, G.J.; Pitcher, E.J.; Ferguson, P.D.

    1995-01-01

    Optimizing the neutronic performance of a coupled-moderator system for a Long-Pulse Spallation Source is a new and challenging area for the spallation target-system designer. For optimal performance of a neutron source, it is essential to have good communication with instrument scientists to obtain proper design criteria and continued interaction with mechanical, thermal-hydraulic, and materials engineers to attain a practical design. A good comprehension of the basics of coupled-moderator neutronics will aid in the proper design of a target system for a Long-Pulse Spallation Source

  13. Coupled nonlinear oscillators

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, J; Scott, A C

    1983-01-01

    Topics discussed include transitions in weakly coupled nonlinear oscillators, singularly perturbed delay-differential equations, and chaos in simple laser systems. Papers are presented on truncated Navier-Stokes equations in a two-dimensional torus, on frequency locking in Josephson point contacts, and on soliton excitations in Josephson tunnel junctions. Attention is also given to the nonlinear coupling of radiation pulses to absorbing anharmonic molecular media, to aspects of interrupted coarse-graining in stimulated excitation, and to a statistical analysis of long-term dynamic irregularity in an exactly soluble quantum mechanical model.

  14. Apodized coupled resonator waveguides.

    Science.gov (United States)

    Capmany, J; Muñoz, P; Domenech, J D; Muriel, M A

    2007-08-06

    In this paper we propose analyse the apodisation or windowing of the coupling coefficients in the unit cells of coupled resonator waveguide devices (CROWs) as a means to reduce the level of secondary sidelobes in the bandpass characteristic of their transfer functions. This technique is regularly employed in the design of digital filters and has been applied as well in the design of other photonic devices such as corrugated waveguide filters and fiber Bragg gratings. The apodisation of both Type-I and Type-II structures is discussed for several windowing functions.

  15. Coupling in reflector arrays

    DEFF Research Database (Denmark)

    Appel-Hansen, Jørgen

    1968-01-01

    In order to reduce the space occupied by a reflector array, it is desirable to arrange the array antennas as close to each other as possible; however, in this case coupling between the array antennas will reduce the reflecting properties of the reflector array. The purpose of the present communic......In order to reduce the space occupied by a reflector array, it is desirable to arrange the array antennas as close to each other as possible; however, in this case coupling between the array antennas will reduce the reflecting properties of the reflector array. The purpose of the present...

  16. Induced Smectic X Phase Through Intermolecular Hydrogen-Bonded Liquid Crystals Formed Between Citric Acid and p- n-(Octyloxy)Benzoic Acid

    Science.gov (United States)

    Sundaram, S.; Subhasri, P.; Rajasekaran, T. R.; Jayaprakasam, R.; Senthil, T. S.; Vijayakumar, V. N.

    2017-08-01

    Hydrogen-bonded liquid crystal (HBLC) is synthesized from citric acid (CA) and 4-(octyloxy)benzoic acid (8OBA) with different mole ratios. Fourier transform infrared spectroscopy (FT-IR) confirms the presence of hydrogen bond between CA and 8OBA. Nuclear magnetic resonance (NMR) spectroscopic studies validate the intermolecular complementary, cyclic type of hydrogen bond, and molecular environment in the designed HBLC complex. Powder X-ray diffraction analysis reveals the monoclinic nature of liquid crystal complex in solid phase. Liquid crystal parameters such as phase transition temperature and enthalpy values for the corresponding mesogenic phases are investigated using a polarizing optical microscope (POM) and differential scanning calorimetry (DSC). It is observed that the change in chain length and steric hindrance while increasing the mole ratio in HBLC complex induces a new smectic X (Sm X) along with higher-order smectic G (Sm G) phases by quenching of smectic C (Sm C). From the experimental observations, induced Sm X phase has been identified as a finger print texture. Also, Sm G is a multi-colored mosaic texture in 1:1, 1:2, and 1:3 mol ratios. The optical tilt angle, thermal stability factor, and enhanced thermal span width of CA + 8OBA complex are discussed.

  17. Detailed intermolecular structure of molecular liquids containing slightly distorted tetrahedral molecules with C(3v) symmetry: chloroform, bromoform, and methyl-iodide.

    Science.gov (United States)

    Pothoczki, Szilvia; Temleitner, László; Pusztai, László

    2011-01-28

    Analyses of the intermolecular structure of molecular liquids containing slightly distorted tetrahedral molecules of the CXY(3)-type are described. The process is composed of the determination of several different distance-dependent orientational correlation functions, including ones that are introduced here. As a result, a complete structure classification could be provided for CXY(3) molecular liquids, namely for liquid chloroform, bromoform, and methyl-iodide. In the present work, the calculations have been conducted on particle configurations resulting from reverse Monte Carlo computer modeling: these particle arrangements have the advantage that they are fully consistent with structure factors from neutron and x-ray diffraction measurements. It has been established that as the separation between neighboring molecules increases, the dominant mutual orientations change from face-to-face to edge-to-edge, via the edge-to-face arrangements. Depending on the actual liquid, these geometrical elements (edges and faces of the distorted tetrahedra) were found to contain different atoms. From the set of liquids studied here, the structure of methyl-iodide was found to be easiest to describe on the basis of pure steric effects (molecular shape, size, and density) and the structure of liquid chloroform seems to be the furthest away from the corresponding "flexible fused hard spheres" like reference system.

  18. Intermolecular effects on the radiogenic formation of electron-capture phosphorus-centered radicals. A single-crystal ESR study of diastereoisomeric precursors

    Energy Technology Data Exchange (ETDEWEB)

    Aagaard, O.M.; Janssen, R.A.J.; de Waal, B.F.M.; Buck, H.M. (Eindhoven Univ. of Technology (Netherlands))

    1990-01-31

    ESR experiments on X-irradiated single crystals of the 2R,4S,5R and 2S,4S,5R diastereoisomers of 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide reveal that the yield of radiogenic electron-capture reactions in the solid state strongly depends on intermolecular interactions in the crystal. In the present case a high yield of P-Cl three-electron-bond phosphoranyl radical anions is found in crystals of the 2R,4S,5R isomer, whereas no radical formation can be detected for the 2S,4S,5R isomer. An analysis of nonbonded interactions with neighboring molecules reveals that the geometry relaxation necessary for the radical stabilization is easily accommodated in crystals of the 2R,4S,SR isomer but not in the 2S,4S,5R isomer, explaining the observed difference in electron-capture efficiency. Experiments on radical formation in a MeTHF host matrix give further insight into the importance of the environment on radiogenic radical formation. The possible concurrent effect of the matrix on the electronic configuration and spin density distribution of the resulting phosphoranyl radical is discussed.

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

    Science.gov (United States)

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

    2013-02-28

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-09

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

  1. Intermolecular effects on the radiogenic formation of electron-capture phosphorus-centered radicals. A single-crystal ESR study of diastereoisomeric precursors

    International Nuclear Information System (INIS)

    Aagaard, O.M.; Janssen, R.A.J.; de Waal, B.F.M.; Buck, H.M.

    1990-01-01

    ESR experiments on X-irradiated single crystals of the 2R,4S,5R and 2S,4S,5R diastereoisomers of 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide reveal that the yield of radiogenic electron-capture reactions in the solid state strongly depends on intermolecular interactions in the crystal. In the present case a high yield of P-Cl three-electron-bond phosphoranyl radical anions is found in crystals of the 2R,4S,5R isomer, whereas no radical formation can be detected for the 2S,4S,5R isomer. An analysis of nonbonded interactions with neighboring molecules reveals that the geometry relaxation necessary for the radical stabilization is easily accommodated in crystals of the 2R,4S,SR isomer but not in the 2S,4S,5R isomer, explaining the observed difference in electron-capture efficiency. Experiments on radical formation in a MeTHF host matrix give further insight into the importance of the environment on radiogenic radical formation. The possible concurrent effect of the matrix on the electronic configuration and spin density distribution of the resulting phosphoranyl radical is discussed

  2. Long-stem shaped multifunctional molecular beacon for highly sensitive nucleic acids determination via intramolecular and intermolecular interactions based strand displacement amplification.

    Science.gov (United States)

    Xu, Jianguo; Zheng, Tingting; Le, Jingqing; Jia, Lee

    2017-11-20

    Occurrence and application of oligonucleotide probes have promoted great progress in the biochemical analysis field due to their unique biological and chemical properties. In this work, a long-stem shaped multifunctional molecular beacon (LS-MMB) that is responsive to a cancer-related gene, p53, is well-prepared. By designing the probe with long-paired bases at its two ends and short-paired bases between the middle region and the 3' end, the LS-MMB is intelligently endowed with the ability to recognize the target analyte, serve as the polymerization primer/template, and signal the hybridization event synchronously, which is distinctly advantageous over the traditional molecular beacons (MBs). Moreover, it is excitingly found that the LS-MMB can be employed to exert intramolecular and intermolecular interactions for strand displacement amplification (SDA) without the involvement of any assistant probes; this therapy results in a really easy and rapid sensing system that provides an extremely low background noise and high target output signal. In this case, an excellent sensitivity and specificity to detect target gene down to picomolar level and resolution to even one nucleotide variation are achieved, respectively. In addition, the application potential for real genomic DNA analysis is realized. We envision that the probe of LS-MMB can act as a universal platform for biosensing and biomedical research.

  3. Simulations of molecular self-assembled monolayers on surfaces: packing structures, formation processes and functions tuned by intermolecular and interfacial interactions.

    Science.gov (United States)

    Wen, Jin; Li, Wei; Chen, Shuang; Ma, Jing

    2016-08-17

    Surfaces modified with a functional molecular monolayer are essential for the fabrication of nano-scale electronics or machines with novel physical, chemical, and/or biological properties. Theoretical simulation based on advanced quantum chemical and classical models is at present a necessary tool in the development, design, and understanding of the interfacial nanostructure. The nanoscale surface morphology, growth processes, and functions are controlled by not only the electronic structures (molecular energy levels, dipole moments, polarizabilities, and optical properties) of building units but also the subtle balance between intermolecular and interfacial interactions. The switchable surfaces are also constructed by introducing stimuli-responsive units like azobenzene derivatives. To bridge the gap between experiments and theoretical models, opportunities and challenges for future development of modelling of ferroelectricity, entropy, and chemical reactions of surface-supported monolayers are also addressed. Theoretical simulations will allow us to obtain important and detailed information about the structure and dynamics of monolayer modified interfaces, which will guide the rational design and optimization of dynamic interfaces to meet challenges of controlling optical, electrical, and biological functions.

  4. The experimental charge-density approach in the evaluation of intermolecular interactions. Application of a new module of the XD programming package to several solids including a pentapeptide.

    Science.gov (United States)

    Abramov, Y A; Volkov, A; Wu, G; Coppens, P

    2000-11-01

    A new module interfaced to the XD programming package has been used in the evaluation of intermolecular interactions and lattice energies of the crystals of p-nitroaniline, L-asparagine monohydrate and the pentapeptide Boc-Gln-D-Iva-Hyp-Ala-Phol (Boc = butoxycarbonyl, Iva = isovaline = ethylalanine, Phol = phenylalaninol). The electrostatic interactions are evaluated with the atom-centered distributed multipoles from KRMM (kappa'-restricted multipole model) refinements, using the Buckingham expression for non-overlapping charge densities. Results for p-nitroaniline are compared with Hartree-Fock (HF), density functional (DFT) and Moller-Plesset (MP2) supermolecular calculations and with HF and DFT periodic calculations. The HF and DFT methods fail to predict the stability of the p-nitroaniline crystal but the results of the experimental charge-density approach (ECDA) are in good agreement with both MP2 interaction energies and the experimental lattice energy. ECDA results for L-asparagine monohydrate compare well with those from DFT supermolecular and periodic HF calculations. The disorder of the terminal group in the pentapeptide, which persists at the experimental temperature of 20 K, corresponds to an energy difference of only 0.35 kJ mol(-1), which is too small to be reproduced with current methods.

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

    International Nuclear Information System (INIS)

    Pashynska, Vlada; Stepanian, Stepan; Gömöry, Agnes; Vekey, Karoly; Adamowicz, Ludwik

    2015-01-01

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

  6. 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.

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

    Science.gov (United States)

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

    2005-12-01

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

  8. ElectroWeak Bosons Couplings

    CERN Document Server

    Ouraou, Ahmimed; The ATLAS collaboration

    2016-01-01

    Latest results on the measurement of gauge boson couplings, from ATLAS and CMS at the LHC, are presented. This review starts with an introduction to boson couplings, then the measurements of Triple and Quartic Couplings are described. And finally, limits on anomalous couplings are summarized.

  9. Dynamics of coupled electron-nuclei-systems in laser fields; Dynamik gekoppelter Elektronen-Kern-Systeme in Laserfeldern

    Energy Technology Data Exchange (ETDEWEB)

    Falge, Mirjam

    2012-07-01

    -resolved photoelectron spectra and the influence of non-adiabatic effects in this asymmetry were investigated. In the last part of this work, the dynamics and optical control in spin-coupled vibronic states were analysed.

  10. Bond-order wave phase of the extended Hubbard model: Electronic solitons, paramagnetism, and coupling to Peierls and Holstein phonons

    Science.gov (United States)

    Kumar, Manoranjan; Soos, Zoltán G.

    2010-10-01

    The bond-order wave (BOW) phase of the extended Hubbard model (EHM) in one dimension (1D) is characterized at intermediate correlation U=4t by exact treatment of N -site systems. Linear coupling to lattice (Peierls) phonons and molecular (Holstein) vibrations are treated in the adiabatic approximation. The molar magnetic susceptibility χM(T) is obtained directly up to N=10 . The goal is to find the consequences of a doubly degenerate ground state (gs) and finite magnetic gap Em in a regular array. Degenerate gs with broken inversion symmetry are constructed for finite N for a range of V near the charge-density-wave boundary at V≈2.18t where Em≈0.5t is large. The electronic amplitude B(V) of the BOW in the regular array is shown to mimic a tight-binding band with small effective dimerization δeff . Electronic spin and charge solitons are elementary excitations of the BOW phase and also resemble topological solitons with small δeff . Strong infrared intensity of coupled molecular vibrations in dimerized 1D systems is shown to extend to the regular BOW phase while its temperature dependence is related to spin solitons. The Peierls instability to dimerization has novel aspects for degenerate gs and substantial Em that suppresses thermal excitations. Finite Em implies exponentially small χM(T) at low temperature followed by an almost linear increase with T . The EHM with U=4t is representative of intermediate correlations in quasi-1D systems such as conjugated polymers or organic ion-radical and charge-transfer salts. The vibronic and thermal properties of correlated models with BOW phases are needed to identify possible physical realizations.

  11. Anomalous top magnetic couplings

    Indian Academy of Sciences (India)

    2012-11-09

    Nov 9, 2012 ... Corresponding author. E-mail: remartinezm@unal.edu.co. Abstract. The real and imaginary parts of the one-loop electroweak contributions to the left and right tensorial anomalous couplings of the tbW vertex in the Standard Model (SM) are computed. Keywords. Top; anomalous. PACS Nos 14.65.Ha; 12.15 ...

  12. HIV-discordant couples

    African Journals Online (AJOL)

    Winnie

    2006-06-02

    Jun 2, 2006 ... These may broadly be divided into factors that affect the transmissibility of HIV between couples per sex act and factors influencing the number of sex acts during which exposure may occur. Examples of the former include use of condoms or other barrier methods and certain sexual behaviours, such as sex.

  13. Gravitationally coupled electroweak monopole

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Y.M., E-mail: ymcho7@konkuk.ac.kr [Administration Building 310-4, Konkuk University, Seoul 143-701 (Korea, Republic of); School of Physics and Astronomy, Seoul National University, Seoul 151-742 (Korea, Republic of); Kimm, Kyoungtae [Faculty of Liberal Education, Seoul National University, Seoul 151-747 (Korea, Republic of); Yoon, J.H. [Department of Physics, College of Natural Sciences, Konkuk University, Seoul 143-701 (Korea, Republic of)

    2016-10-10

    We present a family of gravitationally coupled electroweak monopole solutions in Einstein–Weinberg–Salam theory. Our result confirms the existence of globally regular gravitating electroweak monopole which changes to the magnetically charged black hole as the Higgs vacuum value approaches to the Planck scale. Moreover, our solutions could provide a more accurate description of the monopole stars and magnetically charged black holes.

  14. International Migration of Couples

    DEFF Research Database (Denmark)

    Junge, Martin; Munk, Martin D.; Nikolka, Till

    2018-01-01

    Migrant self-selection is important to labor markets and public finances in both origin and destination countries. We develop a theoretical model regarding the migration of dual-earner couples and test it using population-wide administrative data from Denmark. Our model predicts that the probabil...

  15. Warthog: Coupling Status Update

    Energy Technology Data Exchange (ETDEWEB)

    Hart, Shane W. D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Reardon, Bradley T. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-06-30

    The Warthog code was developed to couple codes that are developed in both the Multi-Physics Object-Oriented Simulation Environment (MOOSE) from Idaho National Laboratory (INL) and SHARP from Argonne National Laboratory (ANL). The initial phase of this work, focused on coupling the neutronics code PROTEUS with the fuel performance code BISON. The main technical challenge involves mapping the power density solution determined by PROTEUS to the fuel in BISON. This presents a challenge since PROTEUS uses the MOAB mesh format, but BISON, like all other MOOSE codes, uses the libMesh format. When coupling the different codes, one must consider that Warthog is a light-weight MOOSE-based program that uses the Data Transfer Kit (DTK) to transfer data between the various mesh types. Users set up inputs for the codes they want to run, and then Warthog transfers the data between them. Currently Warthog supports XSProc from SCALE or the Sub-Group Application Programming Interface (SGAPI) in PROTEUS for generating cross sections. It supports arbitrary geometries using PROTEUS and BISON. DTK will transfer power densities and temperatures between the codes where the domains overlap. In the past fiscal year (FY), much work has gone into demonstrating two-way coupling for simple pin cells of various materials. XSProc was used to calculate the cross sections, which were then passed to PROTEUS in an external file. PROTEUS calculates the fission/power density, and Warthog uses DTK to pass this information to BISON, where it is used as the heat source. BISON then calculates the temperature profile of the pin cell and sends it back to XSProc to obtain the temperature corrected cross sections. This process is repeated until the convergence criteria (tolerance on BISON solve, or number of time steps) is reached. Models have been constructed and run for both uranium oxide and uranium silicide fuels. These models demonstrate a clear difference in power shape that is not accounted for in a

  16. Optically coupled semiconductor device

    Energy Technology Data Exchange (ETDEWEB)

    Kumagaya, Naoki

    1988-11-18

    This invention concerns an optically coupled semiconductor device using the light as input signal and a MOS transistor for the output side in order to control on-off of the output side by the input signal which is insulated from the output. Concerning this sort of element, when a MOS transistor and a load resistance are planned to be accumulated on the same chip, a resistor and control of impurity concentration of the channel, etc. become necessary despite that the only formation of a simple P-N junction is enough, for a solar cell, hence cost reduction thereof cannot be done. In order to remove this defect, this invention offers an optically coupled semiconductor device featuring that two solar cells are connected in reverse parallel between the gate sources of the output MOS transistors and an operational light emitting element is individually set facing a respective solar cell. 4 figs.

  17. Magnetic coupling device

    Science.gov (United States)

    Nance, Thomas A [Aiken, SC

    2009-08-18

    A quick connect/disconnect coupling apparatus is provided in which a base member is engaged by a locking housing through a series of interengagement pins. The pins maintain the shaft in a locked position. Upon exposure to an appropriately positioned magnetic field, pins are removed a sufficient distance such that the shaft may be withdrawn from the locking housing. The ability to lock and unlock the connector assembly requires no additional tools or parts apart from a magnetic key.

  18. Coupling of Hidden Sector

    OpenAIRE

    Królikowski, Wojciech

    2016-01-01

    A hypothetic Hidden Sector of the Universe, consisting of sterile fer\\-mions (``sterinos'') and sterile mediating bosons (``sterons'') of mass dimension 1 (not 2!) --- the last described by an antisymmetric tensor field --- requires to exist also a scalar isovector and scalar isoscalar in order to be able to construct electroweak invariant coupling (before spontaneously breaking its symmetry). The introduced scalar isoscalar might be a resonant source for the diphoton excess of 750 GeV, sugge...

  19. Quick torque coupling

    Science.gov (United States)

    Luft, Peter A [El Cerrito, CA

    2009-05-12

    A coupling for mechanically connecting modular tubular struts of a positioning apparatus or space frame, comprising a pair of toothed rings (10, 12) attached to separate strut members (16), the teeth (18, 20) of the primary rings (10, 12) mechanically interlocking in both an axial and circumferential manner, and a third part comprising a sliding, toothed collar (14) the teeth (22) of which interlock the teeth (18, 20) of the primary rings (10, 12), preventing them from disengaging, and completely locking the assembly together. A secondary mechanism provides a nesting force for the collar, and/or retains it. The coupling is self-contained and requires no external tools for installation, and can be assembled with gloved hands in demanding environments. No gauging or measured torque is required for assembly. The assembly can easily be visually inspected to determine a "go" or "no-go" status. The coupling is compact and relatively light-weight. Because of it's triply interlocking teeth, the connection is rigid. The connection does not primarily rely on clamps, springs or friction based fasteners, and is therefore reliable in fail-safe applications.

  20. Coupling and decoupling

    International Nuclear Information System (INIS)

    Ravenal, E.C.

    1988-01-01

    This paper reports on the prospects of coupling and decoupling for extended deterrence. Thirty-eight years after the foundation of NATO, the defence of Western Europe still rests on the proposition that an American president will invite the destruction of US cities and the incineration of 100 million of its citizens to repel a Soviet incursion or resist a Soviet ultimatum in Western Europe. On its face, America's war plan---never denied by any president from Truman to Reagan, or by any Secretary of State from George Marshall to George Shultz---is the first use of nuclear weapons, if necessary, to defend Europe. Thus America threatens to turn local defeat into global holocaust. But under the surface, America's nuclear commitment to Europe is not so sure. The word that encapsulates this problem is coupling. Not the title of an Updike novel or an anthropological treatise by Margaret Mead, coupling is a term of art used by strategic analysts to connote the integrity of the chain of escalation, from conventional war in Europe, to theatre nuclear weapons, to the final use of America's ultimate strategic weapon

  1. Coupled-resonator optical waveguides

    DEFF Research Database (Denmark)

    Raza, Søren; Grgic, Jure; Pedersen, Jesper Goor

    2010-01-01

    Coupled-resonator optical waveguides hold potential for slow-light propagation of optical pulses. The dispersion properties may adequately be analyzed within the framework of coupled-mode theory. We extend the standard coupled-mode theory for such structures to also include complex-valued paramet......Coupled-resonator optical waveguides hold potential for slow-light propagation of optical pulses. The dispersion properties may adequately be analyzed within the framework of coupled-mode theory. We extend the standard coupled-mode theory for such structures to also include complex...

  2. High-resolution 1H NMR spectroscopy of fish muscle, eggs and small whole fish via Hadamard-encoded intermolecular multiple-quantum coherence.

    Directory of Open Access Journals (Sweden)

    Honghao Cai

    Full Text Available BACKGROUND AND PURPOSE: Nuclear magnetic resonance (NMR spectroscopy has become an important technique for tissue studies. Since tissues are in semisolid-state, their high-resolution (HR spectra cannot be obtained by conventional NMR spectroscopy. Because of this restriction, extraction and high-resolution magic angle spinning (HR MAS are widely applied for HR NMR spectra of tissues. However, both of the methods are subject to limitations. In this study, the feasibility of HR (1H NMR spectroscopy based on intermolecular multiple-quantum coherence (iMQC technique is explored using fish muscle, fish eggs, and a whole fish as examples. MATERIALS AND METHODS: Intact salmon muscle tissues, intact eggs from shishamo smelt and a whole fish (Siamese algae eater are studied by using conventional 1D one-pulse sequence, Hadamard-encoded iMQC sequence, and HR MAS. RESULTS: When we use the conventional 1D one-pulse sequence, hardly any useful spectral information can be obtained due to the severe field inhomogeneity. By contrast, HR NMR spectra can be obtained in a short period of time by using the Hadamard-encoded iMQC method without shimming. Most signals from fatty acids and small metabolites can be observed. Compared to HR MAS, the iMQC method is non-invasive, but the resolution and the sensitivity of resulting spectra are not as high as those of HR MAS spectra. CONCLUSION: Due to the immunity to field inhomogeneity, the iMQC technique can be a proper supplement to HR MAS, and it provides an alternative for the investigation in cases with field distortions and with samples unsuitable for spinning. The acquisition time of the proposed method is greatly reduced by introduction of the Hadamard-encoded technique, in comparison with that of conventional iMQC method.

  3. ReaxFF molecular dynamics simulation of intermolecular structure formation in acetic acid-water mixtures at elevated temperatures and pressures

    Science.gov (United States)

    Sengul, Mert Y.; Randall, Clive A.; van Duin, Adri C. T.

    2018-04-01

    The intermolecular structure formation in liquid and supercritical acetic acid-water mixtures was investigated using ReaxFF-based molecular dynamics simulations. The microscopic structures of acetic acid-water mixtures with different acetic acid mole fractions (1.0 ≥ xHAc ≥ 0.2) at ambient and critical conditions were examined. The potential energy surface associated with the dissociation of acetic acid molecules was calculated using a metadynamics procedure to optimize the dissociation energy of ReaxFF potential. At ambient conditions, depending on the acetic acid concentration, either acetic acid clusters or water clusters are dominant in the liquid mixture. When acetic acid is dominant (0.4 ≤ xHAc), cyclic dimers and chain structures between acetic acid molecules are present in the mixture. Both structures disappear at increased water content of the mixture. It was found by simulations that the acetic acid molecules released from these dimer and chain structures tend to stay in a dipole-dipole interaction. These structural changes are in agreement with the experimental results. When switched to critical conditions, the long-range interactions (e.g., second or fourth neighbor) disappear and the water-water and acetic acid-acetic acid structural formations become disordered. The simulated radial distribution function for water-water interactions is in agreement with experimental and computational studies. The first neighbor interactions between acetic acid and water molecules are preserved at relatively lower temperatures of the critical region. As higher temperatures are reached in the critical region, these interactions were observed to weaken. These simulations indicate that ReaxFF molecular dynamics simulations are an appropriate tool for studying supercritical water/organic acid mixtures.

  4. Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Witte, Jonathon [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Neaton, Jeffrey B. [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720 (United States); Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2016-05-21

    With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions—noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms—with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methods and systems examined, the most complete basis is Jensen’s pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. A sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems.

  5. Model for an RNA tertiary interaction from the structure of an intermolecular complex between a GAAA tetraloop and an RNA helix.

    Science.gov (United States)

    Pley, H W; Flaherty, K M; McKay, D B

    1994-11-03

    In large structured RNAs, RNA hairpins in which the strands of the duplex stem are connected by a tetraloop of the consensus sequence 5'-GNRA (where N is any nucleotide, and R is either G or A) are unusually frequent. In group I introns there is a covariation in sequence between nucleotides in the third and fourth positions of the loop with specific distant base pairs in putative RNA duplex stems: GNAA loops correlate with successive 5'-C-C.G-C base pairs in stems, whereas GNGA loops correlate with 5'-C-U.G-A. This has led to the suggestion that GNRA tetraloops may be involved in specific long-range tertiary interactions, with each A in position 3 or 4 of the loop interacting with a C-G base pair in the duplex, and G in position 3 interacting with a U-A base pair. This idea is supported experimentally for the GAAA loop of the P5b extension of the group I intron of Tetrahymena thermophila and the L9 GUGA terminal loop of the td intron of bacteriophage T4 (ref. 4). NMR has revealed the overall structure of the tetraloop for 12-nucleotide hairpins with GCAA and GAAA loops and models have been proposed for the interaction of GNRA tetraloops with base pairs in the minor groove of A-form RNA. Here we describe the crystal structure of an intermolecular complex between a GAAA tetraloop and an RNA helix. The interactions we observe correlate with the specificity of GNRA tetraloops inferred from phylogenetic studies, suggesting that this complex is a legitimate model for intramolecular tertiary interactions mediated by GNRA tetraloops in large structured RNAs.

  6. Crystal structure of the anti-(carcinoembryonic antigen) single-chain Fv antibody MFE-23 and a model for antigen binding based on intermolecular contacts.

    Science.gov (United States)

    Boehm, M K; Corper, A L; Wan, T; Sohi, M K; Sutton, B J; Thornton, J D; Keep, P A; Chester, K A; Begent, R H; Perkins, S J

    2000-03-01

    MFE-23 is the first single-chain Fv antibody molecule to be used in patients and is used to target colorectal cancer through its high affinity for carcinoembryonic antigen (CEA), a cell-surface member of the immunoglobulin superfamily. MFE-23 contains an N-terminal variable heavy-chain domain joined by a (Gly(4)Ser)(3) linker to a variable light-chain (V(L)) domain (kappa chain) with an 11-residue C-terminal Myc-tag. Its crystal structure was determined at 2.4 A resolution by molecular replacement with an R(cryst) of 19.0%. Five of the six antigen-binding loops, L1, L2, L3, H1 and H2, conformed to known canonical structures. The sixth loop, H3, displayed a unique structure, with a beta-hairpin loop and a bifurcated apex characterized by a buried Thr residue. In the crystal lattice, two MFE-23 molecules were associated back-to-back in a manner not seen before. The antigen-binding site displayed a large acidic region located mainly within the H2 loop and a large hydrophobic region within the H3 loop. Even though this structure is unliganded within the crystal, there is an unusually large region of contact between the H1, H2 and H3 loops and the beta-sheet of the V(L) domain of an adjacent molecule (strands DEBA) as a result of intermolecular packing. These interactions exhibited remarkably high surface and electrostatic complementarity. Of seven MFE-23 residues predicted to make contact with antigen, five participated in these lattice contacts, and this model for antigen binding is consistent with previously reported site-specific mutagenesis of MFE-23 and its effect on CEA binding.

  7. Heteroleptic and Homoleptic Iron(III Spin-Crossover Complexes; Effects of Ligand Substituents and Intermolecular Interactions between Co-Cation/Anion and the Complex

    Directory of Open Access Journals (Sweden)

    Wasinee Phonsri

    2017-08-01

    Full Text Available The structural and magnetic properties of a range of new iron(III bis-tridentate Schiff base complexes are described with emphasis on how intermolecular structural interactions influence spin states and spin crossover (SCO in these d5 materials. Three pairs of complexes were investigated. The first pair are the neutral, heteroleptic complexes [Fe(3-OMe-SalEen(thsa] 1 and [Fe(3-MeOSalEen(3-EtOthsa] 2, where 3-R-HSalEen = (E-2-(((2-(ethylaminoethyliminomethyl-6-R-phenol and 3-R-H2thsa = thiosemicarbazone-3-R-salicylaldimine. They display spin transitions above room temperature. However, 2 shows incomplete and gradual change, while SCO in 1 is complete and more abrupt. Lower cooperativity in 2 is ascribed to the lack of π–π interactions, compared to 1. The second pair, cationic species [Fe(3-EtOSalEen2]NO3 3 and [Fe(3-EtOSalEen2]Cl 4 differ only in the counter-anion. They show partial SCO above room temperature with 3 displaying a sharp transition at 343 K. Weak hydrogen bonds from cation to Cl− probably lead to weaker cooperativity in 4. The last pair, CsH2O[Fe(3-MeO-thsa2] 5 and Cs(H2O2[Fe(5-NO2-thsa2] 6, are anionic homoleptic chelates that have different substituents on the salicylaldiminate rings of thsa2−. The Cs cations bond to O atoms of water and the ligands, in unusual ways thus forming attractive 1D and 3D networks in 5 and 6, respectively, and 5 remains HS (high spin at all temperatures while 6 remains LS (low spin. Comparisons are made to other literature examples of Cs salts of [Fe(5-R-thsa2]− (R = H and Br.

  8. Effect of Group Cognitive Behavioral Couples Therapy on Couple Burnout and Divorce Tendency in Couples

    Directory of Open Access Journals (Sweden)

    M Mohammadi

    2017-02-01

    Full Text Available Background & aim: Couple burnout is one of the phenomena which involve many couples, it is among the main causes of emotional divorce, and without proper management and treatment, and it can lay the ground for formal divorce among couples. Cognitive behavioral couple therapy is one of the existing approaches in the couple therapy field, the efficiency of which has been established for resolving many marital problems. The present study was designed by the aim of investigating the effect of group cognitive behavioral couple therapy on couple burnout and divorce tendency in couples.   Methods: The present research was of applied research type. The research method was semi-empirical with a pretest-posttest with control group design. The research population included all the couples with marital conflict and problems who, after a recall announcement of the researcher, visited the counseling and psychological services center located in Gorgan city in 2014. By using the available sampling method, 20 couples were selected among the volunteer and qualified couples for the research, and they were assigned into experiment and control groups (10 couples per group by random assignment. In the present research, the Pines burnout questionnaire (1996 and divorce tendency scale of Rouswelt, Johnson, and Mouro (1986 were used for gathering the data. After taking the pretest, the group cognitive behavioral couple therapy based on the couple therapy model of Baucom  and colleagues (2008 was held in 10 2-hour weekly sessions for the experiment group couples, while the control group couples received no intervention. The data were analyzed through descriptive statistics method and multivariate covariance analysis (MANCOVA in SPSS v.20. Results: The multivariate covariance analysis results for couple burnout (F= 28.80 and divorce tendency (F= 51.25 suggested that there was a significant difference between the couples of experiment and control groups (P< 0

  9. Intermolecular Interactions at high pressure

    DEFF Research Database (Denmark)

    Eikeland, Espen Zink

    2016-01-01

    In this project high-pressure single crystal X-ray diffraction has been combined with quantitative energy calculations to probe the energy landscape of three hydroquinone clathrates enclosing different guest molecules. The simplicity of the hydroquinone clathrate structures together with their st...

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

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, R.M.

    1986-11-01

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

  11. Loosely coupled class families

    DEFF Research Database (Denmark)

    Ernst, Erik

    2001-01-01

    are expressed using virtual classes seem to be very tightly coupled internally. While clients have achieved the freedom to dynamically use one or the other family, it seems that any given family contains a xed set of classes and we will need to create an entire family of its own just in order to replace one...... of the members with another class. This paper shows how to express class families in such a manner that the classes in these families can be used in many dierent combinations, still enabling family polymorphism and ensuring type safety....

  12. LIA longitudinal coupling impedance

    International Nuclear Information System (INIS)

    Faltens, A.

    1980-01-01

    The beam generated fields enter into the problems of waveform generation and longitudinal stability. In the former, provision must be made for the longitudinally defocusing forces due to the space charge and the beam loading effects on the accelerating voltage due to the current of a presumably known bunch. In the latter, the concern is for the growth of unintentional perturbations to unacceptably large values through the interaction of the charge and current fluctuations with the rest of the beam and the surrounding structures. These beam generated electric fields may be related to the beam current through a coupling impedance

  13. Interpreting the nonlinear dielectric response of glass-formers in terms of the coupling model

    International Nuclear Information System (INIS)

    Ngai, K. L.

    2015-01-01

    Nonlinear dielectric measurements at high electric fields of glass-forming glycerol and propylene carbonate initially were carried out to elucidate the dynamic heterogeneous nature of the structural α-relaxation. Recently, the measurements were extended to sufficiently high frequencies to investigate the nonlinear dielectric response of faster processes including the so-called excess wing (EW), appearing as a second power law at high frequencies in the loss spectra of many glass formers without a resolved secondary relaxation. While a strong increase of dielectric constant and loss is found in the nonlinear dielectric response of the α-relaxation, there is a lack of significant change in the EW. A surprise to the experimentalists finding it, this difference in the nonlinear dielectric properties between the EW and the α-relaxation is explained in the framework of the coupling model by identifying the EW investigated with the nearly constant loss (NCL) of caged molecules, originating from the anharmonicity of the intermolecular potential. The NCL is terminated at longer times (lower frequencies) by the onset of the primitive relaxation, which is followed sequentially by relaxation processes involving increasing number of molecules until the terminal Kohlrausch α-relaxation is reached. These intermediate faster relaxations, combined to form the so-called Johari-Goldstein (JG) β-relaxation, are spatially and dynamically heterogeneous, and hence exhibit nonlinear dielectric effects, as found in glycerol and propylene carbonate, where the JG β-relaxation is not resolved and in D-sorbitol where it is resolved. Like the linear susceptibility, χ 1 (f), the frequency dispersion of the third-order dielectric susceptibility, χ 3 (f), was found to depend primarily on the α-relaxation time, and independent of temperature T and pressure P. I show this property of the frequency dispersions of χ 1 (f) and χ 3 (f) is the characteristic of the many-body relaxation

  14. Nonminimally coupled hybrid inflation

    International Nuclear Information System (INIS)

    Koh, Seoktae; Minamitsuji, Masato

    2011-01-01

    We discuss the hybrid inflation model where the inflaton field is nonminimally coupled to gravity. In the Jordan frame, the potential contains φ 4 term as well as terms in the original hybrid inflation model. In our model, inflation can be classified into the type (I) and the type (II). In the type (I), inflation is terminated by the tachyonic instability of the waterfall field, while in the type (II) by the violation of slow-roll conditions. In our model, the reheating takes place only at the true minimum and even in the case (II) finally the tachyonic instability occurs after the termination of inflation. For a negative nonminimal coupling, inflation takes place in the vacuum-dominated region, in the large field region, or near the local minimum/maximum. Inflation in the vacuum-dominated region becomes either the type (I) or (II), resulting in a blue or red spectrum of the curvature perturbations, respectively. Inflation around the local maximum can be either the type (I) or the type (II), which results in the red spectrum of the curvature perturbations, while around the local minimum it must be the type (I), which results in the blue spectrum. In the large field region, to terminate inflation, potential in the Einstein frame must be positively tilted, always resulting in the red spectrum. We then numerically solve the equations of motion to investigate the whole dynamics of inflaton and confirm that the spectrum of curvature perturbations changes from red to blue ones as scales become smaller.

  15. Strong Coupling Holography

    CERN Document Server

    Dvali, Gia

    2009-01-01

    We show that whenever a 4-dimensional theory with N particle species emerges as a consistent low energy description of a 3-brane embedded in an asymptotically-flat (4+d)-dimensional space, the holographic scale of high-dimensional gravity sets the strong coupling scale of the 4D theory. This connection persists in the limit in which gravity can be consistently decoupled. We demonstrate this effect for orbifold planes, as well as for the solitonic branes and string theoretic D-branes. In all cases the emergence of a 4D strong coupling scale from bulk holography is a persistent phenomenon. The effect turns out to be insensitive even to such extreme deformations of the brane action that seemingly shield 4D theory from the bulk gravity effects. A well understood example of such deformation is given by large 4D Einstein term in the 3-brane action, which is known to suppress the strength of 5D gravity at short distances and change the 5D Newton's law into the four-dimensional one. Nevertheless, we observe that the ...

  16. How couples choose vasectomy.

    Science.gov (United States)

    Schehl, M

    1997-01-01

    A study conducted by AVSC International between 1992 and 1995 found that couples around the world go through a highly similar decision-making process when they choose vasectomy as their family planning methods. Study findings are based upon in-depth, qualitative interviews with couples using vasectomy in Bangladesh, Mexico, Kenya, and Rwanda, where the prevalence of vasectomy is relatively low, and Sri Lanka and the US, where it is relatively high. 218 separate interviews were conducted with male and female partners. Concerns about the woman's health were cited by respondents in each country as reasons to cease childbearing and to opt for vasectomy as the means to achieving that end. Also, almost all respondents mentioned varying degrees of financial hardship as contributing to their decision to end childbearing. These findings highlight the concept of partnership in relationships and family planning decision-making, and demonstrate the importance of going beyond traditional stereotypes about gender roles in decision-making. Social influences and the potential risks of using other forms of contraception also contributed to the choice of using vasectomy. The decision-making process and lessons learned are discussed.

  17. Magnetically Coupled Calorimeters

    Science.gov (United States)

    Bandler, Simon

    2011-01-01

    Calorimeters that utilize the temperature sensitivity of magnetism have been under development for over 20 years. They have targeted a variety of different applications that require very high resolution spectroscopy. I will describe the properties of this sensor technology that distinguish it from other low temperature detectors and emphasize the types of application to which they appear best suited. I will review what has been learned so far about the best materials, geometries, and read-out amplifiers and our understanding of the measured performance and theoretical limits. I will introduce some of the applications where magnetic calorimeters are being used and also where they are in development for future experiments. So far, most magnetic calorimeter research has concentrated on the use of paramagnets to provide temperature sensitivity; recent studies have also focused on magnetically coupled calorimeters that utilize the diamagnetic response of superconductors. I will present some of the highlights of this research, and contrast the properties of the two magnetically coupled calorimeter types.

  18. Using the Model Coupling Toolkit to couple earth system models

    Science.gov (United States)

    Warner, J.C.; Perlin, N.; Skyllingstad, E.D.

    2008-01-01

    Continued advances in computational resources are providing the opportunity to operate more sophisticated numerical models. Additionally, there is an increasing demand for multidisciplinary studies that include interactions between different physical processes. Therefore there is a strong desire to develop coupled modeling systems that utilize existing models and allow efficient data exchange and model control. The basic system would entail model "1" running on "M" processors and model "2" running on "N" processors, with efficient exchange of model fields at predetermined synchronization intervals. Here we demonstrate two coupled systems: the coupling of the ocean circulation model Regional Ocean Modeling System (ROMS) to the surface wave model Simulating WAves Nearshore (SWAN), and the coupling of ROMS to the atmospheric model Coupled Ocean Atmosphere Prediction System (COAMPS). Both coupled systems use the Model Coupling Toolkit (MCT) as a mechanism for operation control and inter-model distributed memory transfer of model variables. In this paper we describe requirements and other options for model coupling, explain the MCT library, ROMS, SWAN and COAMPS models, methods for grid decomposition and sparse matrix interpolation, and provide an example from each coupled system. Methods presented in this paper are clearly applicable for coupling of other types of models. ?? 2008 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2008-03-17

    structure splittings for complex 3. This behavior is thought to be due to the onset of short-range magnetic correlations/coherences between molecules caused by weak intermolecular magnetic exchange interactions.

  20. Fluid structure coupling algorithm

    International Nuclear Information System (INIS)

    McMaster, W.H.; Gong, E.Y.; Landram, C.S.; Quinones, D.F.

    1980-01-01

    A fluid-structure-interaction algorithm has been developed and incorporated into the two-dimensional code PELE-IC. This code combines an Eulerian incompressible fluid algorithm with a Lagrangian finite element shell algorithm and incorporates the treatment of complex free surfaces. The fluid structure and coupling algorithms have been verified by the calculation of solved problems from the literature and from air and steam blowdown experiments. The code has been used to calculate loads and structural response from air blowdown and the oscillatory condensation of steam bubbles in water suppression pools typical of boiling water reactors. The techniques developed have been extended to three dimensions and implemented in the computer code PELE-3D

  1. COUPLED CHEMOTAXIS FLUID MODEL

    KAUST Repository

    LORZ, ALEXANDER

    2010-06-01

    We consider a model system for the collective behavior of oxygen-driven swimming bacteria in an aquatic fluid. In certain parameter regimes, such suspensions of bacteria feature large-scale convection patterns as a result of the hydrodynamic interaction between bacteria. The presented model consist of a parabolicparabolic chemotaxis system for the oxygen concentration and the bacteria density coupled to an incompressible Stokes equation for the fluid driven by a gravitational force of the heavier bacteria. We show local existence of weak solutions in a bounded domain in d, d = 2, 3 with no-flux boundary condition and in 2 in the case of inhomogeneous Dirichlet conditions for the oxygen. © 2010 World Scientific Publishing Company.

  2. Coupled wave sensor technology

    International Nuclear Information System (INIS)

    Maki, M.C.

    1988-01-01

    Buried line guided radar sensors have been used successfully for a number of years to provide perimeter security for high value resources. This paper introduces a new complementary sensor advancement at Computing Devices termed 'coupled wave device technology' (CWD). It provides many of the inherent advantages of leakey cable sensors, such as terrain-following and the ability to discriminate between humans and small animals. It also is able to provide a high or wide detection zone, and allows the sensor to be mounted aerially and adjacent to a wall or fence. Several alternative sensors have been developed which include a single-line sensor, a dual-line hybrid sensor that combines the elements of ported coax and CWD technology, and a rapid-deployment portable sensor for temporary or mobile applications. A description of the technology, the sensors, and their characteristics is provided

  3. Structural Coupling and Translation

    DEFF Research Database (Denmark)

    Tække, Jesper

    formations. After presenting the two theories the article put forward Twitter as an example making it possible to compare the two theories. Hereby the article also provides two analysis of how Twitter changes the communication milieu of modern society. In systems theory media can be seen as the mechanisms...... and translations the social medium of Twitter opens for. The second, but most prioritized, aim of the paper is to present, compare and discuss the two theories: How do they understand what becomes visible in their different optics, which observations become possible in the one or the other – and is it possible...... creating networks consisting in both humans and non-humans. Then the two appearing frameworks are used to observe Twitter and discuss which structural couplings and translations are made possible by this medium. In the end of the paper the two theories are discussed and compared....

  4. Atomic motions in the αβ-region of glass-forming polymers: molecular versus mode coupling theory approach

    International Nuclear Information System (INIS)

    Colmenero, Juan; Narros, Arturo; Alvarez, Fernando; Arbe, Arantxa; Moreno, Angel J

    2007-01-01

    We present fully atomistic molecular dynamics simulation results on a main-chain polymer, 1,4-polybutadiene, in the merging region of the α- and β-relaxations. A real-space analysis reveals the occurrence of localized motions ('β-like') in addition to the diffusive structural relaxation. A molecular approach provides a direct connection between the local conformational changes reflected in the atomic motions and the secondary relaxations in this polymer. Such local processes occur just in the time window where the β-process of the mode coupling theory is expected. We show that the application of this theory is still possible and yields an unusually large value of the exponent parameter. This result might originate from the competition between two mechanisms for dynamic arrest: intermolecular packing and intramolecular barriers for local conformational changes ('β-like')

  5. Gay and lesbian couples in Italy: comparisons with heterosexual couples.

    Science.gov (United States)

    Antonelli, Paolo; Dèttore, Davide; Lasagni, Irene; Snyder, Douglas K; Balderrama-Durbin, Christina

    2014-12-01

    Assessing couple relationships across diverse languages and cultures has important implications for both clinical intervention and prevention. This is especially true for nontraditional relationships potentially subject to various expressions of negative societal evaluation or bias. Few empirically validated measures of relationship functioning have been developed for cross-cultural applications, and none have been examined for their psychometric sufficiency for evaluating same-sex couples across different languages and cultures. The current study examined the psychometric properties of an Italian translation of the Marital Satisfaction Inventory - Revised (MSI-R), a 150-item 13-scale measure of couple relationship functioning, for its use in assessing the intimate relationships of gay and lesbian couples in Italy. Results for these couples were compared to data from heterosexual married and unmarried cohabiting couples from the same geographical region, as well as to previously published data for gay, lesbian, and unmarried heterosexual couples from the United States. Findings suggest that, despite unique societal pressures confronting Italian same-sex couples, these relationships appear resilient and fare well both overall and in specific domains of functioning compared to heterosexual couples both in Italy and the United States. © 2014 Family Process Institute.

  6. 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.

  7. Mössbauer spectroscopic and powder X-ray diffraction studies on incorporation of gaseous organic molecules into intermolecular nano-voids of mixed-valence trinuclear iron pentafluorobenzoate complex

    International Nuclear Information System (INIS)

    Sakai, Yoichi; Onaka, Satoru; Ogiso, Ryo; Takayama, Tsutomu; Takahashi, Masashi; Nakamoto, Tadahiro

    2013-01-01

    Incorporation of gaseous organic molecules into polycrystalline mixed-valence trinuclear iron (Fe 3+ ,Fe 3+ ,Fe 2+ ) pentafluorobenzoate complex Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 with intermolecular nano-voids was studied by 57 Fe-Mössbauer spectroscopic and powder XRD measurements. Organic-molecule incorporation was mainly chased by using iron-valence fluctuation observed in a Mössbauer spectrum, and also researched supportively by a powder XRD technique. (author)

  8. Synchronizability of coupled PWL maps

    International Nuclear Information System (INIS)

    Polynikis, A.; Di Bernardo, M.; Hogan, S.J.

    2009-01-01

    In this paper we discuss the phenomenon of synchronization of chaotic systems in the case of coupled piecewise linear (PWL) continuous and discontinuous one-dimensional maps. We present numerical results for two examples of coupled systems consisting of two PWL maps. We illustrate how the coupled system can achieve synchronization and discuss the nature of the bifurcation that occurs at a critical value of the coupling strength. We then determine this critical coupling using linear stability analysis. We discuss the effects of variation of the parameters of the PWL maps on the critical coupling and present different bifurcation scenarios obtained for different sets of values of these parameters. Finally, we discuss an extension of our work to the synchronizability of networks consisting of two or more PWL maps. We show how the synchronizability of a network of PWL maps can be improved by tuning the map parameters.

  9. Phosphorus As a Simultaneous Electron-Pair Acceptor in Intermolecular P center dot center dot center dot N Pnicogen Bonds and Electron-Pair Donor to Lewis Acids

    Czech Academy of Sciences Publication Activity Database

    Del Bene, J. E.; Alkorta, I.; Sanchez-Sanz, Goar; Elguero, J.

    2013-01-01

    Roč. 117, č. 14 (2013), s. 3133-3141 ISSN 1089-5639 Institutional support: RVO:61388963 Keywords : spin coupling-constants * Gaussian-basis sets * correlated molecular calculations * noncovalent interaction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.775, year: 2013

  10. ESPC Coupled Global Prediction System

    Science.gov (United States)

    2015-09-30

    through an improvement to the sea ice albedo . Fig. 3: 2-m Temperature bias (deg C) of 120-h forecasts for the month of May 2014 for the Arctic...forecast system (NAVGEM) and ocean- sea ice forecast system (HYCOM/CICE) have never been coupled at high resolution. The coupled processes will be...winds and currents across the interface. The sea - ice component of this project requires modification of CICE versions 4 and 5 to run in the coupled

  11. Cosmological tests of coupled Galileons

    International Nuclear Information System (INIS)

    Brax, Philippe; Burrage, Clare; Davis, Anne-Christine; Gubitosi, Giulia

    2015-01-01

    We investigate the cosmological properties of Galileon models which admit Minkowski space as a stable solution in vacuum. This is motivated by stable, positive tension brane world constructions that give rise to Galileons. We include both conformal and disformal couplings to matter and focus on constraints on the theory that arise because of these couplings. The disformal coupling to baryonic matter is extremely constrained by astrophysical and particle physics effects. The disformal coupling to photons induces a cosmological variation of the speed of light and therefore distorsions of the Cosmic Microwave Background spectrum which are known to be very small. The conformal coupling to baryons leads to a variation of particle masses since Big Bang Nucleosynthesis which is also tightly constrained. We consider the background cosmology of Galileon models coupled to Cold Dark Matter (CDM), photons and baryons and impose that the speed of light and particle masses respect the observational bounds on cosmological time scales. We find that requiring that the equation of state for the Galileon models must be close to -1 now restricts severely their parameter space and can only be achieved with a combination of the conformal and disformal couplings. This leads to large variations of particle masses and the speed of light which are not compatible with observations. As a result, we find that cosmological Galileon models are viable dark energy theories coupled to dark matter but their couplings, both disformal and conformal, to baryons and photons must be heavily suppressed making them only sensitive to CDM

  12. Instabilities in strongly coupled plasmas

    CERN Document Server

    Kalman, G J

    2003-01-01

    The conventional Vlasov treatment of beam-plasma instabilities is inappropriate when the plasma is strongly coupled. In the strongly coupled liquid state, the strong correlations between the dust grains fundamentally affect the conditions for instability. In the crystalline state, the inherent anisotropy couples the longitudinal and transverse polarizations, and results in unstable excitations in both polarizations. We summarize analyses of resonant and non-resonant, as well as resistive instabilities. We consider both ion-dust streaming and dust beam-plasma instabilities. Strong coupling, in general, leads to an enhancement of the growth rates. In the crystalline phase, a resonant transverse instability can be excited.

  13. Spin reorientation via antiferromagnetic coupling

    Energy Technology Data Exchange (ETDEWEB)

    Ranjbar, M., E-mail: mojtaba.ranjbar@physics.gu.se [Data Storage Institute, A-STAR (Agency for Science, Technology and Research), 5, Engineering Drive 1, Singapore 117608 (Singapore); Department of Physics, University of Gothenburg, 412 96 Gothenburg (Sweden); Sbiaa, R. [Data Storage Institute, A-STAR (Agency for Science, Technology and Research), 5, Engineering Drive 1, Singapore 117608 (Singapore); Department of Physics, Sultan Qaboos University, P.O. Box 36, PC 123, Muscat (Oman); Dumas, R. K. [Department of Physics, University of Gothenburg, 412 96 Gothenburg (Sweden); Åkerman, J. [Department of Physics, University of Gothenburg, 412 96 Gothenburg (Sweden); Materials Physics, School of ICT, Royal Institute of Technology (KTH), 164 40 Kista (Sweden); Piramanayagam, S. N. [Data Storage Institute, A-STAR (Agency for Science, Technology and Research), 5, Engineering Drive 1, Singapore 117608 (Singapore)

    2014-05-07

    Spin reorientation in antiferromagnetically coupled (AFC) Co/Pd multilayers, wherein the thickness of the constituent Co layers was varied, was studied. AFC-Co/Pd multilayers were observed to have perpendicular magnetic anisotropy even for a Co sublayer thickness of 1 nm, much larger than what is usually observed in systems without antiferromagnetic coupling. When similar multilayer structures were prepared without antiferromagnetic coupling, this effect was not observed. The results indicate that the additional anisotropy energy contribution arising from the antiferromagnetic coupling, which is estimated to be around 6 × 10{sup 6} ergs/cm{sup 3}, induces the spin-reorientation.

  14. Performance assessment of coupled processes

    International Nuclear Information System (INIS)

    Pigford, T.H.

    1987-01-01

    The author considers all processes to be coupled. For example, a waste package heats the surrounding rock and its pore water, creating gradients in density and pressure that result in increased water flow. That process can be described as coupled, in that the flow is a consequence of heating. In a narrower sense, one speaks also of the more weakly coupled transport processes, expressed by the Onsager reciprocal relations, that state that a transport current, i.e., flux, of heat is accompanied by a small transport current of material, as evidenced in isotope separation by thermal diffusion, the Thompson effect in thermoelectricity, etc. This paper presents a performance assessment of coupled processes

  15. Stirring Strongly Coupled Plasma

    CERN Document Server

    Fadafan, Kazem Bitaghsir; Rajagopal, Krishna; Wiedemann, Urs Achim

    2009-01-01

    We determine the energy it takes to move a test quark along a circle of radius L with angular frequency w through the strongly coupled plasma of N=4 supersymmetric Yang-Mills (SYM) theory. We find that for most values of L and w the energy deposited by stirring the plasma in this way is governed either by the drag force acting on a test quark moving through the plasma in a straight line with speed v=Lw or by the energy radiated by a quark in circular motion in the absence of any plasma, whichever is larger. There is a continuous crossover from the drag-dominated regime to the radiation-dominated regime. In the crossover regime we find evidence for significant destructive interference between energy loss due to drag and that due to radiation as if in vacuum. The rotating quark thus serves as a model system in which the relative strength of, and interplay between, two different mechanisms of parton energy loss is accessible via a controlled classical gravity calculation. We close by speculating on the implicati...

  16. Coupling detrended fluctuation analysis for analyzing coupled nonstationary signals

    Science.gov (United States)

    Hedayatifar, L.; Vahabi, M.; Jafari, G. R.

    2011-08-01

    When many variables are coupled to each other, a single case study could not give us thorough and precise information. When these time series are stationary, different methods of random matrix analysis and complex networks can be used. But, in nonstationary cases, the multifractal-detrended-cross-correlation-analysis (MF-DXA) method was introduced for just two coupled time series. In this article, we have extended the MF-DXA to the method of coupling detrended fluctuation analysis (CDFA) for the case when more than two series are correlated to each other. Here, we have calculated the multifractal properties of the coupled time series, and by comparing CDFA results of the original series with those of the shuffled and surrogate series, we can estimate the source of multifractality and the extent to which our series are coupled to each other. We illustrate the method by selected examples from air pollution and foreign exchange rates.

  17. Coupled assimilation for an intermediated coupled ENSO prediction model

    Science.gov (United States)

    Zheng, Fei; Zhu, Jiang

    2010-10-01

    The value of coupled assimilation is discussed using an intermediate coupled model in which the wind stress is the only atmospheric state which is slavery to model sea surface temperature (SST). In the coupled assimilation analysis, based on the coupled wind-ocean state covariance calculated from the coupled state ensemble, the ocean state is adjusted by assimilating wind data using the ensemble Kalman filter. As revealed by a series of assimilation experiments using simulated observations, the coupled assimilation of wind observations yields better results than the assimilation of SST observations. Specifically, the coupled assimilation of wind observations can help to improve the accuracy of the surface and subsurface currents because the correlation between the wind and ocean currents is stronger than that between SST and ocean currents in the equatorial Pacific. Thus, the coupled assimilation of wind data can decrease the initial condition errors in the surface/subsurface currents that can significantly contribute to SST forecast errors. The value of the coupled assimilation of wind observations is further demonstrated by comparing the prediction skills of three 12-year (1997-2008) hindcast experiments initialized by the ocean-only assimilation scheme that assimilates SST observations, the coupled assimilation scheme that assimilates wind observations, and a nudging scheme that nudges the observed wind stress data, respectively. The prediction skills of two assimilation schemes are significantly better than those of the nudging scheme. The prediction skills of assimilating wind observations are better than assimilating SST observations. Assimilating wind observations for the 2007/2008 La Niña event triggers better predictions, while assimilating SST observations fails to provide an early warning for that event.

  18. Belpex and trilateral market coupling

    International Nuclear Information System (INIS)

    2006-01-01

    This document describes the operation of Belpex, the Belgian power transmission spot market, and its linking with the French (Powernext) and Dutch (APX) auction-style day-ahead spot markets. A last part deals with the extension of this trilateral market to other European countries. Content: Belpex day-ahead market (DAM) (Goals of the DAM: Provide consumers with a wider choice of electrical energy sources, Enable the ARP's to optimize their portfolio in terms of imbalance costs, Reduce trade and credit risks for market players compared with the risks involved in concluding bilateral contracts, Provide economic players with a transparent price benchmark, Stimulate the opening of the electricity market); Market model Product (description, Contracts, Collateral calculation, From 12 January to launch date Corporate and Legal Aspects, Next developments); Trilateral Market Coupling (What is market coupling and what are the benefits?, Implementation of trilateral market coupling ('TLC') in France/Belgium/Netherlands, From Trilateral to Multilateral, Implementation of Trilateral Market Coupling (TLC) in France/Belgium/Netherlands, Decentralized market coupling mechanism, influence of import and export on area prices); Decentralized market coupling (2 countries Situations: unconstrained/constrained, Decentralized market coupling: 3 countries, High Level Properties of Market Coupling, Maximize flow until prices across link converge (or ATC limit reached), Power flows from low price area to high price area, Implementing a decentralized technical approach, Market Coupling Daily Process, Impact on Existing Exchange Arrangements, Implementing a decentralized contractual approach, TLC Project Process); From Trilateral to Multilateral (Geographic extensions, Towards an Open and Multilateral Market Coupling, Management of Interconnection Capacities, Interconnection Capacities: current situation, TSO Roles and Responsibilities in the TLC, Other Import/Export products on the

  19. Coupling between minimum scattering antennas

    DEFF Research Database (Denmark)

    Andersen, J.; Lessow, H; Schjær-Jacobsen, Hans

    1974-01-01

    Coupling between minimum scattering antennas (MSA's) is investigated by the coupling theory developed by Wasylkiwskyj and Kahn. Only rotationally symmetric power patterns are considered, and graphs of relative mutual impedance are presented as a function of distance and pattern parameters. Crossed...

  20. Linear analysis of coupled lattices

    Directory of Open Access Journals (Sweden)

    D. Sagan

    1999-07-01

    Full Text Available A formalism for describing the coupled two-dimensional motion of high energy particle beams in a storage ring is developed and extended to circumstances where the coupling is very strong, such as for the Möbius twist accelerator.

  1. Development of Side Coupled Cavities

    International Nuclear Information System (INIS)

    Conto, J.M. de; Carretta, J.M.; Gomez-Martinez, Y.; Micoud, R.

    2008-01-01

    Side coupled Cavities are good candidates for proton accelerations in the 90-180 MeV range, as it has been first proposed for the CERN LINAC4 project. A side coupled Linac is made of a lump chain of resonant cavities, alternatively accelerating and coupling. A side coupled cavity has been designed in a CERN-LPSC collaboration to achieve LINAC4 requirements. After RF studies, a complete thermal study has been done, showing that 10-15% is the absolute maximum duty-cycle achievable by such a cavity. Error studies have been developed. They have shown that a tuning ring is mandatory and that a K equals 3% coupling factor is a good choice. A prototype has been built and each cell has been measured and tuned. A simple and accurate method has been used to get both the resonant frequency and the coupling factor, with a movable tuner and a linear fit. A similar method has been used to get the second order coupling factor. A large dispersion is observed on K. This is mainly due to the shape of the coupling apertures, which are very sensitive to mechanical errors. A future and realistic design must be very careful to guarantee a constant aperture (the important parameter is more the dispersion of k than its exact value). Finally, we analyse how to tune the cavity. This has to checked carefully and probably improved or corrected. Results are expected for mid-2008

  2. Older Couple Relationships and Loneliness

    NARCIS (Netherlands)

    de Jong Gierveld, J.; Broese van Groenou, M.; Bookwala, Jamila

    2016-01-01

    The couple relationship is a major factor in alleviating loneliness. Midlife and older adults without a couple relationship, especially after widowhood or divorce, are at serious risk of loneliness. Outcomes of empirical research, both dating back to the former century (Lopata, 1980, 1996), as well

  3. Slot-Coupled Barbel Antenna

    DEFF Research Database (Denmark)

    Jørgensen, Kasper Lüthje; Jakobsen, Kaj Bjarne

    2016-01-01

    A novel slot-coupled barbel antenna is designed and analyzed. A sensitivity analysis performed in order to improve the bandwidth, while the center frequency is kept constant.......A novel slot-coupled barbel antenna is designed and analyzed. A sensitivity analysis performed in order to improve the bandwidth, while the center frequency is kept constant....

  4. Anisotropic inflation with derivative couplings

    Science.gov (United States)

    Holland, Jonathan; Kanno, Sugumi; Zavala, Ivonne

    2018-05-01

    We study anisotropic power-law inflationary solutions when the inflaton and its derivative couple to a vector field. This type of coupling is motivated by D-brane inflationary models, in which the inflaton, and a vector field living on the D-brane, couple disformally (derivatively). We start by studying a phenomenological model where we show the existence of anisotropic solutions and demonstrate their stability via a dynamical system analysis. Compared to the case without a derivative coupling, the anisotropy is reduced and thus can be made consistent with current limits, while the value of the slow-roll parameter remains almost unchanged. We also discuss solutions for more general cases, including D-brane-like couplings.

  5. Mulliken-Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

    International Nuclear Information System (INIS)

    Rosokha, S.V.; Newton, M.D.; Head-Gordon, M.; Kochi, J.K.

    2006-01-01

    The paramagnetic [1:1] encounter complex (TCNE) 2 -dot is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor (TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE) 2 -dot by its intervalence absorption band at the solvent-dependent wavelength of λ IV ∼1500nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of H DA =1000cm -1 . The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of H DA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy (λ) and the electronic coupling element (H DA ) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes

  6. Couple Discord and Depression in Couples during Couple Therapy and in Depressed Individuals during Depression Treatment

    Science.gov (United States)

    Atkins, David C.; Dimidjian, Sona; Bedics, Jamie D.; Christensen, Andrew

    2009-01-01

    The association between depression and relationship distress as well as the impact of treatment for the one on the other was examined across 2 treatment-seeking samples: individuals seeking treatment for depression (N = 120) and couples seeking marital therapy (N = 134 couples). Although there was a baseline association between depression and…

  7. Improved fluid-structure coupling

    International Nuclear Information System (INIS)

    McMaster, W.H.; Gong, E.Y.; Landram, C.S.

    1981-01-01

    In the computer code PELE-IC, an incompressible Eulerian hydrodynamic algorithm was coupled to a Lagrangian finite element shell algorithm for the analysis of pressure suppression in boiling water reactors. This effort also required the development of a free surface algorithm capable of handling expanding gas bubbles. These algorithms have been improved to strengthen the coupling and to add the capability for following the more complex free surfaces resulting from steam condensation. These improvements have also permitted more economical 2D calculations and have made it feasible to develop a 3D version. A compressible option using the acoustic approximation has also been added, furthering the usefulness of the code. The coupling improvements were made in three areas which are identified as (1) preferential coupling, (2) merged cell coupling, and (3) free surface-structure coupling, and are described. These algorithms have been additionally implemented in a three dimensional version of the code called PELE3D. This version has a free surface capability to follow expanding and contracting bubbles and is coupled to a curved rigid surface

  8. Coupling of the 4f Electrons in Lanthanide Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Kazhdan, Daniel [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    (C5Me5)2LnOTf where Ln = La, Ce, Sm, Gd, and Yb have been synthesized and these derivatives are good starting materials for the synthesis of (C5Me5)2LnX derivatives. (C5Me5)2Ln(2,2'-bipyridine), where Ln = La, Ce, Sm, and Gd, along with several methylated bipyridine analogues have been synthesized and their magnetic moments have been measured as a function of temperature. In lanthanum, cerium, and gadolinium complexes the bipyridine ligand ligand is unequivocally the radical anion, and the observed magnetic moment is the result of intramolecular coupling of the unpaired electron on the lanthanide fragment with the unpaired electron on the bipyridine along with the intermolecular coupling between radicals. Comparison with the magnetic moments of the known compounds (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine) leads to an understanding of the role of the SmII/SmIII and YbII/YbIII couple in the magnetic properties of (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine). In addition, crystal structures of (C5Me5)2Ln(2,2'-bipyridine) and [(C5Me5)2Ln(2,2'-bipyridine)][BPh4](Ln= Ce and Gd), where the lanthanide is unequivocally in the +3 oxidation state, give the crystallographic characteristics of bipyridine as an anion and as a neutral ligand in the same coordination environment, respectively. Substituted bipyridine ligands coordinated to (C5Me5)2Yb are studied to further understand how the magnetic coupling in (C5Me5)2Yb(2,2'-bipyridine) changes with substitutions. In the cases of (C5Me5)2Yb(5,5&apos

  9. Gestural coupling and social cognition

    DEFF Research Database (Denmark)

    Michael, John; Krueger, Joel William

    2012-01-01

    Social cognition researchers have become increasingly interested in the ways that behavioral, physiological, and neural coupling facilitate social interaction and interpersonal understanding. We distinguish two ways of conceptualizing the role of such coupling processes in social cognition: strong...... an essential enabling feature for social interaction and interpersonal understanding more generally and thus ought to exhibit severe deficits in these areas. We challenge SI's prediction and show how MS cases offer compelling reasons for instead adopting MI's pluralistic model of social interaction...... and interpersonal understanding. We conclude that investigations of coupling processes within social interaction should inform rather than marginalize or eliminate investigation of higher-level individual cognition...

  10. Overprotection in couples with aphasia.

    Science.gov (United States)

    Croteau, C; Le Dorze, G

    1999-09-01

    The study aimed to measure the perception of overprotection in 21 couples living with aphasia, relative to controls. The 'Questionnaire on Resources and Stress' assessed the spouses' perception and the 'Overprotection Scale for Adults' measured the perception of persons with aphasia. Husbands of women with aphasia did not differ from husbands of women without aphasia. Wives of men with aphasia reported more overprotection than wives of men without aphasia, even when functional impairment was controlled. The men with aphasia did not report feeling overprotected. No significant relationship was uncovered between the report of overprotection and feeling overprotected in couples with aphasia. Overprotection is present in some couples coping with aphasia.

  11. Anomalous couplings at LEP2

    International Nuclear Information System (INIS)

    Fayolle, D.

    2002-01-01

    In its second phase, LEP has allowed to study four fermion processes never observed before. Results are presented on the charged triple gauge boson couplings (TGC) from the W-pair, Single W and Single γ production. The anomalous quartic gauge couplings (QGC) are constrained using production of WWγ, νν-barγγ and Z γγ final states. Finally, limits on the neutral anomalous gauge couplings (NGC) using the Z γ and ZZ production processes are also reported. All results are consistent with the Standard Model expectations. (authors)

  12. Spatial coupling in heterogeneous catalysis

    Science.gov (United States)

    Yamamoto, S. Y.; Surko, C. M.; Maple, M. B.

    1995-11-01

    Spatial coupling mechanisms are studied in the heterogeneous catalytic oxidation of carbon monoxide over platinum at atmospheric pressure under oscillatory conditions. Experiments are conducted in a continuous flow reactor, and the reaction rate is monitored using both infrared imaging and thermocouples. The catalysts are in the form of platinum annular thin films on washer-shaped quartz substrates, and they provide highly repeatable oscillatory behavior. Oscillations are typically spatially synchronized with the entire catalyst ``flashing'' on and off uniformly. Spatial coupling is investigated by introducing various barriers which split the annular ring in half. Infrared images show that coupling through the gas phase dominates coupling via the diffusion of CO on the surface or heat diffusion through the substrate. The introduction of a localized heat perturbation to the catalyst surface does not induce a transition in the reaction rate. Thus, it is likely that the primary mode of communication is through the gas-phase diffusion of reactants.

  13. Heterogeneous Dynamics of Coupled Vibrations

    NARCIS (Netherlands)

    Cringus, Dan; Jansen, Thomas I. C.; Pshenichnikov, Maxim S.; Schoenlein, RW; Corkum, P; DeSilvestri, S; Nelson, KA; Riedle, E

    2009-01-01

    Frequency-dependent dynamics of coupled stretch vibrations of a water molecule are revealed by 2D IR correlation spectroscopy. These are caused by non-Gaussian fluctuations of the environment around the individual OH stretch vibrations.

  14. Coupling spin qubits via superconductors

    DEFF Research Database (Denmark)

    Leijnse, Martin; Flensberg, Karsten

    2013-01-01

    We show how superconductors can be used to couple, initialize, and read out spatially separated spin qubits. When two single-electron quantum dots are tunnel coupled to the same superconductor, the singlet component of the two-electron state partially leaks into the superconductor via crossed...... Andreev reflection. This induces a gate-controlled singlet-triplet splitting which, with an appropriate superconductor geometry, remains large for dot separations within the superconducting coherence length. Furthermore, we show that when two double-dot singlet-triplet qubits are tunnel coupled...... to a superconductor with finite charging energy, crossed Andreev reflection enables a strong two-qubit coupling over distances much larger than the coherence length....

  15. Cognitive-behavioral couple therapy.

    Science.gov (United States)

    Epstein, Norman B; Zheng, Le

    2017-02-01

    This article describes how cognitive-behavioral couple therapy (CBCT) provides a good fit for intervening with a range of stressors that couples experience from within and outside their relationship. It takes an ecological perspective in which a couple is influenced by multiple systemic levels. We provide an overview of assessment and intervention strategies used to modify negative behavioral interaction patterns, inappropriate or distorted cognitions, and problems with the experience and regulation of emotions. Next, we describe how CBCT can assist couples in coping with stressors involving (a) a partner's psychological disorder (e.g. depression), (b) physical health problems (e.g. cancer), (c) external stressors (e.g. financial strain), and (d) severe relational problems (e.g. partner aggression). Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Common mode and coupled failure

    International Nuclear Information System (INIS)

    Taylor, J.R.

    1975-10-01

    Based on examples and data from Abnormal Occurence Reports for nuclear reactors, a classification of common mode or coupled failures is given, and some simple statistical models are investigated. (author)

  17. Evaluation of Coupled Precipitator Two

    International Nuclear Information System (INIS)

    Stone, M.E.

    1999-01-01

    The offline testing of the Coupled Precipitator Two (CP-2) has been completed. The tests were conducted and are documented. The tests were conducted at an offline test rack near the Drain Tube Test Stand facility in 672-T

  18. Belpex and trilateral market coupling

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-01-15

    This document describes the operation of Belpex, the Belgian power transmission spot market, and its linking with the French (Powernext) and Dutch (APX) auction-style day-ahead spot markets. A last part deals with the extension of this trilateral market to other European countries. Content: Belpex day-ahead market (DAM) (Goals of the DAM: Provide consumers with a wider choice of electrical energy sources, Enable the ARP's to optimize their portfolio in terms of imbalance costs, Reduce trade and credit risks for market players compared with the risks involved in concluding bilateral contracts, Provide economic players with a transparent price benchmark, Stimulate the opening of the electricity market); Market model Product (description, Contracts, Collateral calculation, From 12 January to launch date Corporate and Legal Aspects, Next developments); Trilateral Market Coupling (What is market coupling and what are the benefits?, Implementation of trilateral market coupling ('TLC') in France/Belgium/Netherlands, From Trilateral to Multilateral, Implementation of Trilateral Market Coupling (TLC) in France/Belgium/Netherlands, Decentralized market coupling mechanism, influence of import and export on area prices); Decentralized market coupling (2 countries Situations: unconstrained/constrained, Decentralized market coupling: 3 countries, High Level Properties of Market Coupling, Maximize flow until prices across link converge (or ATC limit reached), Power flows from low price area to high price area, Implementing a decentralized technical approach, Market Coupling Daily Process, Impact on Existing Exchange Arrangements, Implementing a decentralized contractual approach, TLC Project Process); From Trilateral to Multilateral (Geographic extensions, Towards an Open and Multilateral Market Coupling, Management of Interconnection Capacities, Interconnection Capacities: current situation, TSO Roles and Responsibilities in the TLC, Other Import/Export products

  19. Lens Coupled Quantum Cascade Laser

    Science.gov (United States)

    Hu, Qing (Inventor); Lee, Alan Wei Min (Inventor)

    2013-01-01

    Terahertz quantum cascade (QC) devices are disclosed that can operate, e.g., in a range of about 1 THz to about 10 THz. In some embodiments, QC lasers are disclosed in which an optical element (e.g., a lens) is coupled to an output facet of the laser's active region to enhance coupling of the lasing radiation from the active region to an external environment. In other embodiments, terahertz amplifier and tunable terahertz QC lasers are disclosed.

  20. Marital Dissolution Among Interracial Couples

    OpenAIRE

    Zhang, Yuanting; Van Hook, Jennifer

    2009-01-01

    Increases in interracial marriage have been interpreted as reflecting reduced social distance among racial and ethnic groups, but little is known about the stability of interracial marriages. Using six panels of Survey of Income and Program Participation (N = 23,139 married couples), we found that interracial marriages are less stable than endogamous marriages, but these findings did not hold up consistently. After controlling for couple characteristics, the risk of divorce or separation amon...

  1. Coupled Acoustic-Mechanical Bandgaps

    DEFF Research Database (Denmark)

    Jensen, Jakob Søndergaard; Kook, Junghwan

    2016-01-01

    medium and the presence of acoustic resonances. It is demonstrated that corrugation of the plate structure can introduce bending wave bandgaps and bandgaps in the acoustic domain in overlapping and audible frequency ranges. This effect is preserved also when taking the physical coupling between the two...... domains into account. Additionally, the coupling is shown to introduce extra gaps in the band structure due to modal interaction and the appearance of a cut-on frequency for the fundamental acoustic mode....

  2. Development of annular coupled structure

    International Nuclear Information System (INIS)

    Kageyama, T.; Morozumi, Y.; Yoshino, K.; Yamazaki, Y.

    1992-01-01

    A π/2-mode standing-wave linac of an Annular Coupled Structure (ACS) has been developed for the 1-GeV proton linac of the Japanese Hadron Project (JHP). This ACS has four coupling slots between accelerating and coupling cells in order to overcome difficulties in putting the ACS to practical use. Two prototypes of a four-slot ACS (f = 1296 MHz, β = v/c = 0.8) have been constructed and tested: one with a staggered slot-orientation from cell to cell; and the other with a uniform one. The staggered configuration gives a larger coupling constant and a larger shunt impedance than the uniform one with the same size of coupling slot. Both models have been conditioned up to the design input RF power. The four-slot ACS gives a distortion-free accelerating field around the beam axis, while a Side-Coupled Structure cavity gives an accelerating field mixed with a TE111-like mode. (Author) 7 figs., 2 tabs., 9 refs

  3. Fragment-orbital tunneling currents and electronic couplings for analysis of molecular charge-transfer systems.

    Science.gov (United States)

    Hwang, Sang-Yeon; Kim, Jaewook; Kim, Woo Youn

    2018-04-04

    In theoretical charge-transfer research, calculation of the electronic coupling element is crucial for examining the degree of the electronic donor-acceptor interaction. The tunneling current (TC), representing the magnitudes and directions of electron flow, provides a way of evaluating electronic couplings, along with the ability of visualizing how electrons flow in systems. Here, we applied the TC theory to π-conjugated organic dimer systems, in the form of our fragment-orbital tunneling current (FOTC) method, which uses the frontier molecular-orbitals of system fragments as diabatic states. For a comprehensive test of FOTC, we assessed how reasonable the computed electronic couplings and the corresponding TC densities are for the hole- and electron-transfer databases HAB11 and HAB7. FOTC gave 12.5% mean relative unsigned error with regard to the high-level ab initio reference. The shown performance is comparable with that of fragment-orbital density functional theory, which gave the same error by 20.6% or 13.9% depending on the formulation. In the test of a set of nucleobase π stacks, we showed that the original TC expression is also applicable to nondegenerate cases under the condition that the overlap between the charge distributions of diabatic states is small enough to offset the energy difference. Lastly, we carried out visual analysis on the FOTC densities of thiophene dimers with different intermolecular alignments. The result depicts an intimate topological connection between the system geometry and electron flow. Our work provides quantitative and qualitative grounds for FOTC, showing it to be a versatile tool in characterization of molecular charge-transfer systems.

  4. SH2-catalytic domain linker heterogeneity influences allosteric coupling across the SFK family.

    Science.gov (United States)

    Register, A C; Leonard, Stephen E; Maly, Dustin J

    2014-11-11

    Src-family kinases (SFKs) make up a family of nine homologous multidomain tyrosine kinases whose misregulation is responsible for human disease (cancer, diabetes, inflammation, etc.). Despite overall sequence homology and identical domain architecture, differences in SH3 and SH2 regulatory domain accessibility and ability to allosterically autoinhibit the ATP-binding site have been observed for the prototypical SFKs Src and Hck. Biochemical and structural studies indicate that the SH2-catalytic domain (SH2-CD) linker, the intramolecular binding epitope for SFK SH3 domains, is responsible for allosterically coupling SH3 domain engagement to autoinhibition of the ATP-binding site through the conformation of the αC helix. As a relatively unconserved region between SFK family members, SH2-CD linker sequence variability across the SFK family is likely a source of nonredundant cellular functions between individual SFKs via its effect on the availability of SH3 and SH2 domains for intermolecular interactions and post-translational modification. Using a combination of SFKs engineered with enhanced or weakened regulatory domain intramolecular interactions and conformation-selective inhibitors that report αC helix conformation, this study explores how SH2-CD sequence heterogeneity affects allosteric coupling across the SFK family by examining Lyn, Fyn1, and Fyn2. Analyses of Fyn1 and Fyn2, isoforms that are identical but for a 50-residue sequence spanning the SH2-CD linker, demonstrate that SH2-CD linker sequence differences can have profound effects on allosteric coupling between otherwise identical kinases. Most notably, a dampened allosteric connection between the SH3 domain and αC helix leads to greater autoinhibitory phosphorylation by Csk, illustrating the complex effects of SH2-CD linker sequence on cellular function.

  5. Communication and Contraceptive Practices in Adolescent Couples.

    Science.gov (United States)

    Polit-O'Hara, Denise; Kahn, Janet R.

    1985-01-01

    Presents a descriptive analysis of couple communication among stable, sexually active adolescent couples (N=83) and the effect of communication on actual contraceptive practices. Results showed couples with good communication were more likely to practice effective contraception. (BH)

  6. Competing intramolecular N-H⋯O=C hydrogen bonds and extended intermolecular network in 1-(4-chlorobenzoyl)-3-(2-methyl-4-oxopentan-2-yl) thiourea analyzed by experimental and theoretical methods

    Energy Technology Data Exchange (ETDEWEB)

    Saeed, Aamer, E-mail: aamersaeed@yahoo.com [Department of Chemistry, Quaid-I-Azam University, Islamabad 45320 (Pakistan); Khurshid, Asma [Department of Chemistry, Quaid-I-Azam University, Islamabad 45320 (Pakistan); Jasinski, Jerry P. [Department of Chemistry, Keene State College, 229 Main Street Keene, NH 03435-2001 (United States); Pozzi, C. Gustavo; Fantoni, Adolfo C. [Instituto de Física La Plata, Departamento de Física, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 49 y 115, La Plata, Buenos Aires (Argentina); Erben, Mauricio F., E-mail: erben@quimica.unlp.edu.ar [CEQUINOR (UNLP, CONICET-CCT La Plata), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, C.C. 962, (1900) La Plata, Buenos Aires (Argentina)

    2014-03-18

    Highlights: • Two distinct N-H⋯O=C intramolecular competing hydrogen bonds are feasible in the title molecule. • Crystal structures and vibrational properties were determined. • The C=O and C=S double bonds of the acyl-thiourea group are mutually oriented in opposite directions. • A strong hyperconjugative lpO1 → σ{sup ∗}(N2-H) remote interaction was detected. • Topological analysis reveals a Cl⋯N interaction playing a relevant role in crystal packing. - Abstract: The synthesis of a novel 1-acyl-thiourea species (C{sub 14}H{sub 17}N{sub 2}O{sub 2}SCl), has been tailored in such a way that two distinct N-H⋯O=C intramolecular competing hydrogen bonds are feasible. The X-ray structure analysis as well as the vibrational (FT-IR and FT-Raman) data reveal that the S conformation is preferred, with the C=O and C=S bonds of the acyl-thiourea group pointing in opposite directions. The preference for the intramolecular N-H⋯O=C hydrogen bond within the -C(O)NHC(S)NH- core is confirmed. The Natural Bond Orbital and the Atom in Molecule approaches demonstrate that a strong hyperconjugative lpO → σ{sup ∗}(N-H) remote interaction between the acyl and the thioamide N-H groups is responsible for the stabilization of the S conformation. Intermolecular interactions have been characterized in the periodic system electron density and the topological analysis reveals the presence of an extended intermolecular network in the crystal, including a Cl⋯N interaction playing a relevant role in crystal packing.

  7. Cooperativity effect involving drug-DNA/RNA intermolecular interaction: A B3LYP-D3 and MP2 theoretical investigation on ketoprofen⋯cytosine⋯H2O system.

    Science.gov (United States)

    Zhen, Jun-Ping; Wei, Xiao-Chun; Shi, Wen-Jing; Huang, Zhu-Yuan; Jin, Bo; Zhou, Yu-Kun

    2017-11-14

    In order to examine the origin of the drug action and design new DNA/RNA-targeted drugs, the cooperativity effect involving drug-DNA/RNA intermolecular interaction in ketoprofen⋯cytosine⋯H 2 O ternary system were investigated by the B3LYP, B3LYP-D3, and MP2 methods with the 6-311++G(2d,p) basis set. The thermodynamic cooperativity was also evaluated at 310.15 K. The N-H⋯O, O-H⋯O, O-H⋯N, C-H⋯N, and C-H⋯O H bonds coexist in ternary complexes. The intermolecular interactions obtained by B3LYP-D3 are close to those calculated by MP2. The steric effects and van der Waals interactions have little influence on the cooperativity effects. The anti-cooperativity effect in ket⋯cyt⋯H 2 O is far more notable than the cooperativity effect, and the stability of the cyclic structure with anti-cooperativity effect is higher than that of the linear structure with cooperativity effect, as is confirmed by the AIM (atoms in molecules) and RDG (reduced density gradient) analysis. Thus, it can be inferred that, in the presence of H 2 O, the anti-cooperativity effect plays a dominant role in the drug-DNA/RNA interaction, and the nature of the hydration in the binding of drugs to DNA/RNA bases is the H-bonding anti-cooperativity effect. Furthermore, the drug always links simultaneously with DNA/RNA base and H 2 O, and only in this way can the biological activity of drugs play a role. In most cases, the enthalpy change is the major factor driving the cooperativity, as is different from most of biomacromolecule complexes.

  8. Protein-ligand interfaces are polarized: discovery of a strong trend for intermolecular hydrogen bonds to favor donors on the protein side with implications for predicting and designing ligand complexes.

    Science.gov (United States)

    Raschka, Sebastian; Wolf, Alex J; Bemister-Buffington, Joseph; Kuhn, Leslie A

    2018-04-01

    Understanding how proteins encode ligand specificity is fascinating and similar in importance to deciphering the genetic code. For protein-ligand recognition, the combination of an almost infinite variety of interfacial shapes and patterns of chemical groups makes the problem especially challenging. Here we analyze data across non-homologous proteins in complex with small biological ligands to address observations made in our inhibitor discovery projects: that proteins favor donating H-bonds to ligands and avoid using groups with both H-bond donor and acceptor capacity. The resulting clear and significant chemical group matching preferences elucidate the code for protein-native ligand binding, similar to the dominant patterns found in nucleic acid base-pairing. On average, 90% of the keto and carboxylate oxygens occurring in the biological ligands formed direct H-bonds to the protein. A two-fold preference was found for protein atoms to act as H-bond donors and ligand atoms to act as acceptors, and 76% of all intermolecular H-bonds involved an amine donor. Together, the tight chemical and geometric constraints associated with satisfying donor groups generate a hydrogen-bonding lock that can be matched only by ligands bearing the right acceptor-rich key. Measuring an index of H-bond preference based on the observed chemical trends proved sufficient to predict other protein-ligand complexes and can be used to guide molecular design. The resulting Hbind and Protein Recognition Index software packages are being made available for rigorously defining intermolecular H-bonds and measuring the extent to which H-bonding patterns in a given complex match the preference key.

  9. Protein-ligand interfaces are polarized: discovery of a strong trend for intermolecular hydrogen bonds to favor donors on the protein side with implications for predicting and designing ligand complexes

    Science.gov (United States)

    Raschka, Sebastian; Wolf, Alex J.; Bemister-Buffington, Joseph; Kuhn, Leslie A.

    2018-02-01

    Understanding how proteins encode ligand specificity is fascinating and similar in importance to deciphering the genetic code. For protein-ligand recognition, the combination of an almost infinite variety of interfacial shapes and patterns of chemical groups makes the problem especially challenging. Here we analyze data across non-homologous proteins in complex with small biological ligands to address observations made in our inhibitor discovery projects: that proteins favor donating H-bonds to ligands and avoid using groups with both H-bond donor and acceptor capacity. The resulting clear and significant chemical group matching preferences elucidate the code for protein-native ligand binding, similar to the dominant patterns found in nucleic acid base-pairing. On average, 90% of the keto and carboxylate oxygens occurring in the biological ligands formed direct H-bonds to the protein. A two-fold preference was found for protein atoms to act as H-bond donors and ligand atoms to act as acceptors, and 76% of all intermolecular H-bonds involved an amine donor. Together, the tight chemical and geometric constraints associated with satisfying donor groups generate a hydrogen-bonding lock that can be matched only by ligands bearing the right acceptor-rich key. Measuring an index of H-bond preference based on the observed chemical trends proved sufficient to predict other protein-ligand complexes and can be used to guide molecular design. The resulting Hbind and Protein Recognition Index software packages are being made available for rigorously defining intermolecular H-bonds and measuring the extent to which H-bonding patterns in a given complex match the preference key.

  10. Center vortices at strong couplings and all couplings

    International Nuclear Information System (INIS)

    Greensite, J.

    2001-01-01

    Motivations for the center vortex theory of confinement are discussed. In particular, it is noted that the abelian dual Meissner effect, which is the signature of dual superconductivity, cannot adequately describe the confining force at large distance scales. A long-range effective action is derived from strong-coupling lattice gauge theory in D=3 dimensions, and it is shown that center vortices emerge as the stable saddlepoints of this action. Thus, in the case of strong couplings, the vortex picture is arrived at analytically. I also respond briefly to a recent criticism regarding maximal center gauge. (author)

  11. Miscarriage experiences of lesbian couples.

    Science.gov (United States)

    Wojnar, Danuta

    2007-01-01

    This was a descriptive phenomenological study of 10 self-identified lesbian couples who had experienced miscarriage in the context of a committed relationship. Analysis of individual and joint open-ended interviews revealed that the experience of miscarriage for lesbian couples must be viewed from the perspective of the difficulties surrounding conception as well as the actual pregnancy loss. The overarching theme, "We are not in control," captures the struggles lesbian couples faced in conceiving their pregnancies and the sense of loss that accompanied miscarrying. These experiences constituted two sub-themes: "We work so hard to get a baby" and "It hurts so bad: The sorrow of miscarriage." Our results indicate that the experience of miscarriage is compounded by the complexities of planning and achieving pregnancy. Practitioners need to be aware of the unique perspectives lesbian couples have on pregnancy and miscarriage and remain sensitive to their unique needs. Findings may serve as an intervention framework for nurse midwives and others caring for lesbian couples after miscarriage.

  12. Systemic couple therapy for dysthymia.

    Science.gov (United States)

    Montesano, Adrián; Feixas, Guillem; Muñoz, Dámaris; Compañ, Victoria

    2014-03-01

    We examined the effect of Systemic Couple Therapy on a patient diagnosed with dysthymic disorder and her partner. Marge and Peter, a middle-aged married couple, showed significant and meaningful changes in their pattern of interaction over the course of the therapy and, by the end of it, Marge no longer met the diagnostic criteria for dysthymic disorder. Her scores on the Structured Clinical Interview for DSM-IV Axis I Disorders (SCID-I) and Beck Depression Inventory, Second Edition (BDI-II) were in the clinical range before treatment and in the nonclinical one at the end of therapy. Although scores on Dyadic Adjustment Scale showed different patterns, both members reported significant improvement. The analysis of change in the alliance-related behaviors throughout the process concurred with change in couple's pattern of interaction. Treatment effects were maintained at 12-month follow-up. Highlights in the therapy process showed the importance of relational mechanisms of change, such as broadening the therapeutic focus into the couple's pattern of interaction, reducing expressed emotion and resentment, as well as increasing positive exchanges. The results of this evidence-based case study should prompt further investigation of couple therapy for dysthymia disorder. Randomized clinical trial design is needed to reach an evidence-based treatment status. (c) 2014 APA, all rights reserved.

  13. Matter couplings in supergravity theories

    International Nuclear Information System (INIS)

    Bagger, J.A.

    1983-01-01

    The N = 1 supersymmetric nonlinear sigma model is coupled to supergravity. The results are expressed in the language of Kahler geometry. Topological considerations constrain the scalar fields to lie on a Kahler manifold of restricted type, or a Hodge manifold. For topologically nontrivial manifolds, this leads to the quantization of Newton's constant in terms of the scalar self-coupling. The isometries of the N = 1 model are gauged. This gives a geometrical picture of what might be called the gauge invariant supersymmetric nonlinear sigma model. It also provides a new interpretation of the Fayet-Iliopoulos D-term. The gauge invariant supersymmetric nonlinear sigma model is coupled to N = 1 supergravity. This leads to a deeper understanding of the connections between supergravity, R-invariance and the Fayet-Iliopoulos D-term. It also provides a foundation for phenomenological studies of supergravity theories. Finally, the N = 2 supersymmetric nonlinear sigma model is coupled to supergravity. The scalar fields are found to lie on a negatively curved quaternionic manifold. This implies that matter self-couplings that are allowed in N = 2 supersymmetry are forbidden in N = 2 supergravity, and vice versa

  14. String dynamics at strong coupling

    International Nuclear Information System (INIS)

    Hull, C.M.

    1996-01-01

    The dynamics of superstring, supergravity and M-theories and their compactifications are probed by studying the various perturbation theories that emerge in the strong and weak-coupling limits for various directions in coupling constant space. The results support the picture of an underlying non-perturbative theory that, when expanded perturbatively in different coupling constants, gives different perturbation theories, which can be perturbative superstring theories or superparticle theories. The p-brane spectrum is considered in detail and a criterion found to establish which p-branes govern the strong-coupling dynamics. In many cases there are competing conjectures in the literature, and this analysis decides between them. In other cases, new results are found. The chiral 6-dimensional theory resulting from compactifying the type IIB string on K 3 is studied in detail and it is found that certain strong-coupling limits appear to give new theories, some of which hint at the possibility of a 12-dimensional origin. (orig.)

  15. The Effects of Different Electron-Phonon Couplings on the Spectral and Transport Properties of Small Molecule Single-Crystal Organic Semiconductors

    Directory of Open Access Journals (Sweden)

    Carmine Antonio Perroni

    2014-03-01

    Full Text Available Spectral and transport properties of small molecule single-crystal organic semiconductors have been theoretically analyzed focusing on oligoacenes, in particular on the series from naphthalene to rubrene and pentacene, aiming to show that the inclusion of different electron-phonon couplings is of paramount importance to interpret accurately the properties of prototype organic semiconductors. While in the case of rubrene, the coupling between charge carriers and low frequency inter-molecular modes is sufficient for a satisfactory description of spectral and transport properties, the inclusion of electron coupling to both low-frequency inter-molecular and high-frequency intra-molecular vibrational modes is needed to account for the temperature dependence of transport properties in smaller oligoacenes. For rubrene, a very accurate analysis in the relevant experimental configuration has allowed for the clarification of the origin of the temperature-dependent mobility observed in these organic semiconductors. With increasing temperature, the chemical potential moves into the tail of the density of states corresponding to localized states, but this is not enough to drive the system into an insulating state. The mobility along different crystallographic directions has been calculated, including vertex corrections that give rise to a transport lifetime one order of magnitude smaller than the spectral lifetime of the states involved in the transport mechanism. The mobility always exhibits a power-law behavior as a function of temperature, in agreement with experiments in rubrene. In systems gated with polarizable dielectrics, the electron coupling to interface vibrational modes of the gate has to be included in addition to the intrinsic electron-phonon interaction. While the intrinsic bulk electron-phonon interaction affects the behavior of mobility in the coherent regime below room temperature, the coupling with interface modes is dominant for the

  16. Trilateral market coupling. Algorithm appendix

    International Nuclear Information System (INIS)

    2006-03-01

    Market Coupling is both a mechanism for matching orders on the exchange and an implicit cross-border capacity allocation mechanism. Market Coupling improves the economic surplus of the coupled markets: the highest purchase orders and the lowest sale orders of the coupled power exchanges are matched, regardless of the area where they have been submitted; matching results depend however on the Available Transfer Capacity (ATC) between the coupled hubs. Market prices and schedules of the day-ahead power exchanges of the several connected markets are simultaneously determined with the use of the Available Transfer Capacity defined by the relevant Transmission System Operators. The transmission capacity is thereby implicitly auctioned and the implicit cost of the transmission capacity from one market to the other is the price difference between the two markets. In particular, if the transmission capacity between two markets is not fully used, there is no price difference between the markets and the implicit cost of the transmission capacity is null. Market coupling relies on the principle that the market with the lowest price exports electricity to the market with the highest price. Two situations may appear: either the Available Transfer Capacity (ATC) is large enough and the prices of both markets are equalized (price convergence), or the ATC is too small and the prices cannot be equalized. The Market Coupling algorithm takes as an input: 1 - The Available Transfer Capacity (ATC) between each area for each flow direction and each Settlement Period of the following day (i.e. for each hour of following day); 2 - The (Block Free) Net Export Curves (NEC) of each market for each hour of the following day, i.e., the difference between the total quantity of Divisible Hourly Bids and the total quantity of Divisible Hourly Offers for each price level. The NEC reflects a market's import or export volume sensitivity to price. 3 - The Block Orders submitted by the participants in

  17. Chameleons with Field Dependent Couplings

    CERN Document Server

    Brax, Philippe; Mota, David F; Nunes, Nelson J; Winther, Hans A

    2010-01-01

    Certain scalar-tensor theories exhibit the so-called chameleon mechanism, whereby observational signatures of scalar fields are hidden by a combination of self-interactions and interactions with ambient matter. Not all scalar-tensor theories exhibit such a chameleon mechanism, which has been originally found in models with inverse power run-away potentials and field independent couplings to matter. In this paper we investigate field-theories with field-dependent couplings and a power-law potential for the scalar field. We show that the theory indeed is a chameleon field theory. We find the thin-shell solution for a spherical body and investigate the consequences for E\\"ot-Wash experiments, fifth-force searches and Casimir force experiments. Requiring that the scalar-field evades gravitational tests, we find that the coupling is sensitive to a mass-scale which is of order of the Hubble scale today.

  18. Coupled processes in repository sealing

    International Nuclear Information System (INIS)

    Case, J.B.; Kelsall, P.C.

    1985-01-01

    The significance of coupled processes in repository sealing is evaluated. In most repository designs, shaft seals will be located in areas of relatively low temperature perturbation, in which case the coupling of temperature with stress and permeability may be less significant than the coupling between stress and permeability that occurs during excavation. Constitutive relationships between stress and permeability are reviewed for crystalline rock and rocksalt. These provide a basis for predicting the development of disturbed zones near excavations. Field case histories of the degree of disturbance are presented for two contrasting rock types - Stripa granite and Southeastern New Mexico rocksalt. The results of field investigations in both rock types confirm that hydraulic conductivity or permeability is stress dependent, and that shaft seal performance may be related to the degree that stresses are perturbed and restored near the seal

  19. Coupling Functions Enable Secure Communications

    Science.gov (United States)

    Stankovski, Tomislav; McClintock, Peter V. E.; Stefanovska, Aneta

    2014-01-01

    Secure encryption is an essential feature of modern communications, but rapid progress in illicit decryption brings a continuing need for new schemes that are harder and harder to break. Inspired by the time-varying nature of the cardiorespiratory interaction, here we introduce a new class of secure communications that is highly resistant to conventional attacks. Unlike all earlier encryption procedures, this cipher makes use of the coupling functions between interacting dynamical systems. It results in an unbounded number of encryption key possibilities, allows the transmission or reception of more than one signal simultaneously, and is robust against external noise. Thus, the information signals are encrypted as the time variations of linearly independent coupling functions. Using predetermined forms of coupling function, we apply Bayesian inference on the receiver side to detect and separate the information signals while simultaneously eliminating the effect of external noise. The scheme is highly modular and is readily extendable to support different communications applications within the same general framework.

  20. Strong coupling phase in QED

    International Nuclear Information System (INIS)

    Aoki, Ken-ichi

    1988-01-01

    Existence of a strong coupling phase in QED has been suggested in solutions of the Schwinger-Dyson equation and in Monte Carlo simulation of lattice QED. In this article we recapitulate the previous arguments, and formulate the problem in the modern framework of the renormalization theory, Wilsonian renormalization. This scheme of renormalization gives the best understanding of the basic structure of a field theory especially when it has a multi-phase structure. We resolve some misleading arguments in the previous literature. Then we set up a strategy to attack the strong phase, if any. We describe a trial; a coupled Schwinger-Dyson equation. Possible picture of the strong coupling phase QED is presented. (author)