WorldWideScience

Sample records for intermolecular relaxation processes

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Relaxation processes during amorphous metal alloys heating

    International Nuclear Information System (INIS)

    Malinochka, E.Ya.; Durachenko, A.M.; Borisov, V.T.

    1982-01-01

    Behaviour of Te+15 at.%Ge and Fe+13 at.%P+7 at.%C amorphous metal alloys during heating has been studied using the method of differential scanning calorimetry (DSC) as the most convenient one for determination of the value of heat effects, activation energies, temperature ranges of relaxation processes. Thermal effects corresponding to high-temperature relaxation processes taking place during amorphous metal alloys (AMA) heating are detected. The change of ratio of relaxation peaks values on DSC curves as a result of AMA heat treatment can be explained by the presence of a number of levels of inner energy in amorphous system, separated with potential barriers, the heights of which correspond to certain activation energies of relaxation processes

  9. Combining Stochastic Deformation/Relaxation and Intermolecular Contacts Analysis for Extracting Pharmacophores from Ligand-Receptor Complexes.

    Science.gov (United States)

    Hatmal, Ma'mon M; Taha, Mutasem O

    2018-04-23

    We previously combined molecular dynamics (classical or simulated annealing) with ligand-receptor contacts analysis as a means to extract valid pharmacophore model(s) from single ligand-receptor complexes. However, molecular dynamics methods are computationally expensive and time-consuming. Here we describe a novel method for extracting valid pharmacophore model(s) from a single crystallographic structure within a reasonable time scale. The new method is based on ligand-receptor contacts analysis following energy relaxation of a predetermined set of randomly deformed complexes generated from the targeted crystallographic structure. Ligand-receptor contacts maintained across many deformed/relaxed structures are assumed to be critical and used to guide pharmacophore development. This methodology was implemented to develop valid pharmacophore models for PI3K-γ, RENIN, and JAK1. The resulting pharmacophore models were validated by receiver operating characteristic (ROC) analysis against inhibitors extracted from the CHEMBL database. Additionally, we implemented pharmacophores extracted from PI3K-γ to search for new inhibitors from the National Cancer Institute list of compounds. The process culminated in new PI3K-γ/mTOR inhibitory leads of low micromolar IC 50 s.

  10. Capturing molecular multimode relaxation processes in excitable gases based on decomposition of acoustic relaxation spectra

    Science.gov (United States)

    Zhu, Ming; Liu, Tingting; Wang, Shu; Zhang, Kesheng

    2017-08-01

    Existing two-frequency reconstructive methods can only capture primary (single) molecular relaxation processes in excitable gases. In this paper, we present a reconstructive method based on the novel decomposition of frequency-dependent acoustic relaxation spectra to capture the entire molecular multimode relaxation process. This decomposition of acoustic relaxation spectra is developed from the frequency-dependent effective specific heat, indicating that a multi-relaxation process is the sum of the interior single-relaxation processes. Based on this decomposition, we can reconstruct the entire multi-relaxation process by capturing the relaxation times and relaxation strengths of N interior single-relaxation processes, using the measurements of acoustic absorption and sound speed at 2N frequencies. Experimental data for the gas mixtures CO2-N2 and CO2-O2 validate our decomposition and reconstruction approach.

  11. Quantization by stochastic relaxation processes and supersymmetry

    International Nuclear Information System (INIS)

    Kirschner, R.

    1984-01-01

    We show the supersymmetry mechanism resposible for the quantization by stochastic relaxation processes and for the effective cancellation of the additional time dimension against the two Grassmann dimensions. We give a non-perturbative proof of the validity of this quantization procedure. (author)

  12. Impulsive relaxation process in MHD driven reconnection

    International Nuclear Information System (INIS)

    Kitabata, H.; Hayashi, T.; Sato, T.

    1997-01-01

    Compressible magnetohydrodynamic (MHD) simulation is carried out in order to investigate energy relaxation process of the driven magnetic reconnection in an open finite system through a long time calculation. It is found that a very impulsive energy release occurs in an intermittent fashion through magnetic reconnection for a continuous magnetic flux injection on the boundary. We focus our attention on the detailed process in the impulsive phase, which is the reconnection rate is remarkably enhanced up. (author)

  13. gamma. -relaxation process in crystallizable polymers

    Energy Technology Data Exchange (ETDEWEB)

    Mindiyarov, Kh G; Zelenev, Yu V; Bartenev, G M [Birskij Gosudarstvennyj Pedagogicheskij Inst. (USSR)

    1975-07-01

    In the present paper, with the aid of radiothermoluminescence technique ..gamma..-relaxation processes are investigated, which are conditioned by molecular mobility and are associated with defects in the crystalline structure of polymers PEh, PP, and elastomers PIB, NK, SKD, SKI exposed to ..gamma..-rays of Co/sup 60/ at a dose rate of 1 Mrad. The shape of the thermoluminescence curve, i.e. the luminescence intensity in the ..cap alpha.. - ..gamma..-maxima, their relationship, position with respect to temperature are strongly dependent on the degree of crystallinity, on the thermal and mechanical prehistory. In highly crystalline samples of PEh and PP ..cap alpha..-maximum may be absent. Dependence has been studied of the luminescence intensity in the ..cap alpha..- and ..gamma..-maxima (Isub(..cap alpha..)/Isub(..gamma..)) on the crystallization temperature; the curve passes through the minimum when the crystallization rate is maximum. The relationship Isub(..gamma..)re of crystallinity degree.

  14. Effects of distribution function nonequilibrium tails on relaxation and transfer processes in rarefied gases

    International Nuclear Information System (INIS)

    Grigoryev, Yu.N.; Mikhalitsyn, A.N.; Yanenko, N.N.

    1984-01-01

    Quantitative characteristics of the nonmonotone relaxation process are studied in a gas of pseudo-Maxwell molecules. Basic results are obtained by a direct numerical integration of the nonlinear Boltzmann equation. The evolution of initial distributions being finite or having exponential asymptotics of tails was researched. In particular, initial data obtained by selective excitation (absorption) against the Maxwell background encountered in laser physics problems have been considered. It is shown that under conditions of a developed effect of nonmonotone relaxation the overpopulation in the velocity range 4 <= upsilon <= 10 exceeds on the average 2-3 times the equilibrium value. For the given particles energy the excitation is preserved during t = 5/6 and the total relaxation time of the overpopulation wave reaches t asymptotically equals 20. The amplitudes and the relaxation time of overpopulation in the ''cupola'' region of distribution are substantially lower than in the case of a developed effect in the tail. The influence of the effect on the kinetics of threshold chemical reaction is studied. From the results it follows that in the process of nonmonotone relaxation the mean rates of binary threshold reactions can exceed more than twice the equilibrium values. This estimate is valid for all power like intermolecular repulsive potentials from the pseudo-Maxwell model up to rigid spheres. Time intervals over which the mean reaction rate exceeds considerably the equilibrium one make from 5 to 15 mean free path times increasing with the decrease in the potential ''rigidity''. (author)

  15. Models for multiple relaxation processes in collagen fiber

    Indian Academy of Sciences (India)

    ... originate from stress strain induced changes in hydrogen bond network whereas the other seems to be more strongly coupled to salt like bridges and electrostatic interactions. Urea alters the activation energy for one relaxation step while pH and solvent dielectric constant alter the relaxation behavior one set of processes.

  16. Relaxation Processes and Time Scale Transformation.

    Science.gov (United States)

    1982-03-01

    the response function may be immediately recognized as being 14 of the Kubo - Green type in the classical regime. Given this general framework, it is now...b as a function of temperature is 24 equivalent to the Vogel-Beuche-Fulcher empirical law for viscosity or the Williams-Landel-Ferry empirical law...relaxation times. With the weighted sum in the form of an integral , one can write exp(-(t/T)b ] = f dT’g(r’) exp[-(t/T’)], O

  17. 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

  18. A Block-Asynchronous Relaxation Method for Graphics Processing Units

    OpenAIRE

    Anzt, H.; Dongarra, J.; Heuveline, Vincent; Tomov, S.

    2011-01-01

    In this paper, we analyze the potential of asynchronous relaxation methods on Graphics Processing Units (GPUs). For this purpose, we developed a set of asynchronous iteration algorithms in CUDA and compared them with a parallel implementation of synchronous relaxation methods on CPU-based systems. For a set of test matrices taken from the University of Florida Matrix Collection we monitor the convergence behavior, the average iteration time and the total time-to-solution time. Analyzing the r...

  19. Multiple-decker phthalocyaninato dinuclear lanthanoid(III) single-molecule magnets with dual-magnetic relaxation processes.

    Science.gov (United States)

    Katoh, Keiichi; Horii, Yoji; Yasuda, Nobuhiro; Wernsdorfer, Wolfgang; Toriumi, Koshiro; Breedlove, Brian K; Yamashita, Masahiro

    2012-11-28

    The SMM behaviour of dinuclear Ln(III)-Pc multiple-decker complexes (Ln = Tb(3+) and Dy(3+)) with energy barriers and slow-relaxation behaviour were explained by using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of several dinuclear Ln(III)-Pc type SMMs have never been discussed on the basis of the crystal structure. For dinuclear Tb(III)-Pc complexes, a dual magnetic relaxation process was observed. The relaxation processes are due to the anisotropic centres. Our results clearly show that the two Tb(3+) ion sites are equivalent and are consistent with the crystal structure. On the other hand, the mononuclear Tb(III)-Pc complex exhibited only a single magnetic relaxation process. This is clear evidence that the magnetic relaxation mechanism depends heavily on the dipole-dipole (f-f) interactions between the Tb(3+) ions in the dinuclear systems. Furthermore, the SMM behaviour of dinuclear Dy(III)-Pc type SMMs with smaller energy barriers compared with that of Tb(III)-Pc and slow-relaxation behaviour was explained. Dinuclear Dy(III)-Pc SMMs exhibited single-component magnetic relaxation behaviour. The results indicate that the magnetic relaxation properties of dinuclear Ln(III)-Pc multiple-decker complexes are affected by the local molecular symmetry and are extremely sensitive to tiny distortions in the coordination geometry. In other words, the spatial arrangement of the Ln(3+) ions (f-f interactions) in the crystal is important. Our work shows that the SMM properties can be fine-tuned by introducing weak intermolecular magnetic interactions in a controlled SMM spatial arrangement.

  20. Relaxation cracking in the process industry, an underestimated problem

    Energy Technology Data Exchange (ETDEWEB)

    Wortel, J.C. van [TNO Institute of Industrial Technology, Apeldoorn (Netherlands)

    1998-12-31

    Austenitic components, operating between 500 and 750 deg C, can fail within 1 year service while the ordinary mechanical properties after failure are still within the code requirements. The intergranular brittle failures are situated in the welded or cold deformed areas. This type of cracking has many names, showing the uncertainty concerning the mechanism for the (catastrophical) failures. A just finished investigation showed that it is a relaxation crack problem, introduced by manufacturing processes, especially welding and cold rolling. Cracking/failures can be expected after only 0.1- 0.2 % relaxation strain. These low strain values can already be generated during relaxation of the welding stresses. Especially coarse grained `age hardening` materials are susceptible. Stabilising and Postweld Heat Treatments are very effective to avoid relaxation crack problems during operation. After these heat treatments the components can withstand more than 2 % relaxation strain. At temperatures between 500 and 750 deg C relaxation cracking is the predominant factor for the safety and lifetime of welded austenitic components. (orig.) 12 refs.

  1. Relaxation cracking in the process industry, an underestimated problem

    Energy Technology Data Exchange (ETDEWEB)

    Wortel, J.C. van [TNO Institute of Industrial Technology, Apeldoorn (Netherlands)

    1999-12-31

    Austenitic components, operating between 500 and 750 deg C, can fail within 1 year service while the ordinary mechanical properties after failure are still within the code requirements. The intergranular brittle failures are situated in the welded or cold deformed areas. This type of cracking has many names, showing the uncertainty concerning the mechanism for the (catastrophical) failures. A just finished investigation showed that it is a relaxation crack problem, introduced by manufacturing processes, especially welding and cold rolling. Cracking/failures can be expected after only 0.1- 0.2 % relaxation strain. These low strain values can already be generated during relaxation of the welding stresses. Especially coarse grained `age hardening` materials are susceptible. Stabilising and Postweld Heat Treatments are very effective to avoid relaxation crack problems during operation. After these heat treatments the components can withstand more than 2 % relaxation strain. At temperatures between 500 and 750 deg C relaxation cracking is the predominant factor for the safety and lifetime of welded austenitic components. (orig.) 12 refs.

  2. Sawtooth oscillations as MHD relaxation process in a plasma

    International Nuclear Information System (INIS)

    Yoshida, Zensho; Inoue, Nobuyuki; Ogawa, Yuichi

    1992-01-01

    The sawtooth oscillation in a tokamak plasma is a spontaneous relaxation process accompanying global instabilities which behave to reduce the internal magnetic energy. This phenomenon has a similarity to the MHD relaxation processes in Reversed Field Pinch (RFP) and Ultra Low Q (ULQ) plasmas. The self-stabilizing effect of instabilities with m (poloidal mode number) = 1 results in an increase in the central safety factor q(0). Nonlinear dynamics of m = 1 instabilities has been discussed both for global and local modes. The latter appears when a pitch minimum exists in the plasma, and is relevant to the compound sawtooth oscillation. The MHD relaxation is a restructuring process of the plasma current profile that is competitive with the resistive diffusion. (author)

  3. The Effect of Phonon Relaxation Process on Absorption Spectra ...

    African Journals Online (AJOL)

    In this work we study the effect of phonon relaxation process on the absorption spectra using the Green's function technique. The Green's function technique which is widely used in many particle problems is used to solve the Kubo formula which describes the optical absorption process. Finally the configurational diagram is ...

  4. Coherence and relaxation in energy transfer processes in condensed phases

    International Nuclear Information System (INIS)

    Shelby, R.M.

    1978-03-01

    Investigations of electronic triplet and vibrational energy transfer dynamics and relaxation processes are presented. Emphasis is placed on understanding the role of coherence and interactions which tend to destroy the coherence. In the case of triplet excitons at low temperatures, the importance of coherence in energy migration can be established, and the average coherence parameters can be experimentally determined. In the case of vibrational excitations, both picosecond spectroscopic studies of vibrational relaxation and spontaneous Raman spectroscopy are used to characterize the dynamics and give increased insight into the nature of the mechanisms responsible for vibrational dephasing. The design and operation of the picosecond apparatus used in these experiments is also described

  5. An approach to the magnetic relaxation processes in lithium ferrites

    International Nuclear Information System (INIS)

    Torres, C.; Gonzalez Arias, A.; Hernandez-Gomez, P.; Francisco, C. de; Alejos, O.; Munoz, J.M.; Zazo, M.

    2007-01-01

    The relaxation of the initial magnetic permeability has been measured in polycrystalline Li x Fe 3- x O 4 samples, with x ranging from 0 to 0.5, by means of the magnetic disaccommodation (DA) technique. We have found that there is no abrupt transition for a given composition, but there is a progressive modification of the characteristic relaxation processes of magnetite. These results have been interpreted on the basis of the increasing amount of Li ions in the spinel lattice and hence, the resulting modifications on their proximities

  6. 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)

  7. Relaxation processes in aqueous solutions upon X-ray exposure. Entanglement of electronic and nuclear dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Unger, Isaak

    2017-07-01

    About a decade ago new types of electronic non-radiative relaxation processes, involving the environment of an electronically excited or ionized monomer, have been predicted for van der Waals clusters and these were also the first systems where such processes have been detected experimentally. These new autoionization channels encompass the recombination of an electron and a hole, and the energy transfer to a neighboring atom or molecule. Two processes can be distinguished here. In the intermolecular Coulombic decay (ICD) the hole created upon ionization of a monomer is filled by a valence electron of the same species, and the energy released in this electron-hole recombination is used to ionize a neighboring species. In the electron transfer mediated decay (ETMD) the initial hole is filled by an electron from a neighboring species, and the energy released by this recombination is either used to ionize the same neighbor species, or to ionize a third monomer. In more recent experiments on liquid water it has been discovered that these non- local autoionization processes are strongly coupled with ultrafast nuclear dynamics. The core ionization initiates proton motion along a hydrogen donor-bond of the electronically excited water cation. This nuclear dynamics leads to the formation of transient cationic species where a proton is shared by two neighboring water molecules. Subsequent autoionization, either via Auger decay, ICD or ETMD, then occurs from any of such structure transients. This relaxation process is termed proton transfer mediated charge separation, PTM-CS. It has been found in a number of experiments that the probability of PTM-CS to occur depends on the hydrogen-bond strength between the core-ionized molecule and solvent molecules.

  8. Microscopic dynamics and relaxation processes in liquid hydrogen fluoride

    International Nuclear Information System (INIS)

    Angelini, R.; Giura, P.; Monaco, G.; Sette, F.; Fioretto, D.; Ruocco, G.

    2004-01-01

    Inelastic x-ray scattering and Brillouin light scattering measurements of the dynamic structure factor of liquid hydrogen fluoride have been performed in the temperature range T=214-283 K. The data, analyzed using a viscoelastic model with a two time-scale memory function, show a positive dispersion of the sound velocity c(Q) between the low frequency value c 0 (Q) and the high frequency value c ∞α (Q). This finding confirms the existence of a structural (α) relaxation directly related to the dynamical organization of the hydrogen bonds network of the system. The activation energy E a of the process has been extracted by the analysis of the temperature behavior of the relaxation time τ α (T) that follows an Arrhenius law. The obtained value for E a , when compared with that observed in another hydrogen bond liquid as water, suggests that the main parameter governing the α-relaxation process is the number of hydrogen bonds per molecule

  9. Relaxation processes and physical aging in metallic glasses

    Science.gov (United States)

    Ruta, B.; Pineda, E.; Evenson, Z.

    2017-12-01

    Since their discovery in the 1960s, metallic glasses have continuously attracted much interest across the physics and materials science communities. In the forefront are their unique properties, which hold the alluring promise of broad application in fields as diverse as medicine, environmental science and engineering. However, a major obstacle to their wide-spread commercial use is their inherent temporal instability arising from underlying relaxation processes that can dramatically alter their physical properties. The result is a physical aging process which can bring about degradation of mechanical properties, namely through embrittlement and catastrophic mechanical failure. Understanding and controlling the effects of aging will play a decisive role in our on-going endeavor to advance the use of metallic glasses as structural materials, as well as in the more general comprehension of out-of-equilibrium dynamics in complex systems. This review presents an overview of the current state of the art in the experimental advances probing physical aging and relaxation processes in metallic glasses. Similarities and differences between other hard and soft matter glasses are highlighted. The topic is discussed in a multiscale approach, first presenting the key features obtained in macroscopic studies, then connecting them to recent novel microscopic investigations. Particular emphasis is put on the occurrence of distinct relaxation processes beyond the main structural process in viscous metallic melts and their fate upon entering the glassy state, trying to disentangle results and formalisms employed by the different groups of the glass-science community. A microscopic viewpoint is presented, in which physical aging manifests itself in irreversible atomic-scale processes such as avalanches and intermittent dynamics, ascribed to the existence of a plethora of metastable glassy states across a complex energy landscape. Future experimental challenges and the comparison with

  10. Ferromagnetic resonance relaxation processes in Zn2Yt

    International Nuclear Information System (INIS)

    Mita, M.; Shimizu, H.

    1975-01-01

    Experimentally obtained linewidth in FMR of Zn 2 Y is analyzed numerically on the basis of two-magnon, three-magnon and four-magnon relaxation processes. In the analysis procedure of three-magnon linewidth, the effective exchange constants are determined to be D = 0.15 x 10 -9 Oe cm 2 and D = 9.3 x 10 -9 Oe cm 2 within and between the crystallographic planes. The two-magnon linewidth induced by surface imperfections is discussed in consideration of scattering due to multipole demagnetizations of the imperfections. The four-magnon linewidth is observed for the first time and analyzed successfully

  11. On γ-relaxation process in crystallizable polymers

    International Nuclear Information System (INIS)

    Mindiyarov, Kh.G.; Zelenev, Yu.V.; Bartenev, G.M.

    1975-01-01

    In the present paper, with the aid of radiothermoluminescence technique γ-relaxation processes are investigated, which are conditioned by molecular mobility and are associated with defects in the crystalline structure of polymers PEh, PP, and elastomers PIB, NK, SKD, SKI exposed to γ-rays of Co 60 at a dose rate of 1 Mrad. The shape of the thermoluminescence curve, i.e. the luminescence intensity in the α - γ-maxima, their relationship, position with respect to temperature are strongly dependent on the degree of crystallinity, on the thermal and mechanical prehistory. In highly crystalline samples of PEh and PP α-maximum may be absent. Dependence has been studied of the luminescence intensity in the α- and γ-maxima (Isub(α)/Isub(γ)) on the crystallization temperature; the curve passes through the minimum when the crystallization rate is maximum. The relationship Isub(γ)re of crystallinity degree

  12. Anomalous relaxation and self-organization in nonequilibrium processes

    International Nuclear Information System (INIS)

    Fatkullin, Ibrahim; Kladko, Konstantin; Mitkov, Igor; Bishop, A. R.

    2001-01-01

    We study thermal relaxation in ordered arrays of coupled nonlinear elements with external driving. We find that our model exhibits dynamic self-organization manifested in a universal stretched-exponential form of relaxation. We identify two types of self-organization, cooperative and anticooperative, which lead to fast and slow relaxation, respectively. We give a qualitative explanation for the behavior of the stretched exponent in different parameter ranges. We emphasize that this is a system exhibiting stretched-exponential relaxation without explicit disorder or frustration

  13. Continuous relaxation time spectrum of α-process in glass-like B2O3

    International Nuclear Information System (INIS)

    Bartenev, G.M.; Lomovskij, V.A.

    1991-01-01

    α-process of relaxation of glass-like B 2 O 3 was investigated in a wide temperature range. Continuous spectrum of relaxation times H(τ) for this process was constructed, using data of dynamic methods of investigation. It is shown that increase of temperature of α-process investigation leads to change of glass-like BaO 3 structure in such a way, that H(τ) spectrum tends to the maxwell one with a unit relaxation time

  14. Some kinetic and spectroscopic evidence on intramolecular relaxation processes in polyatomic molecules

    International Nuclear Information System (INIS)

    Quack, M.

    1983-01-01

    The description and definition of intramolecular vibrational relaxation processes is discussed within the framework of the quantum mechanical and statistical mechanical equations of motion. The evidence from quite different experimental sources is summarized under the common aspect of vibrational relaxation. Although much of the evidence remains ambiguous, there is good indication that a localized vibrational excitation relaxes typically in 0.1 to 10 picoseconds, which is long compared to many optical and reactive processes

  15. Relaxation processes and structural transformations in amorphous Co-Fe-Si-B alloys

    International Nuclear Information System (INIS)

    Dus-Sitek, M.; Olszowski, Z.

    1994-01-01

    The thermostimulated electron emission (TSEE) method was applied for determination of relaxation and crystallization processes in amorphous alloys. By using the analogy of DTA-method, the activation energy of relaxation and crystallization processes has been determined from the measurements of changes of TSEE temperature maxima depending on the heating rate

  16. Evaluation of biexponential relaxation processes by magnetic resonance imaging. A phantom study

    DEFF Research Database (Denmark)

    Kjaer, L; Thomsen, C; Larsson, H B

    1988-01-01

    Despite the complexity of biologic tissues, a monoexponential behaviour is usually assumed when estimating relaxation processes in vivo by magnetic resonance imaging (MRI). This study was designed to evaluate the potential of biexponential decomposition of T1 and T2 relaxation curves obtained at 1...... echoes. Applying biexponential curve analysis, a significant deviation from a monoexponential behaviour was recognized at a ratio of corresponding relaxation rates of about 3 and 2, estimating T1 and T2 relaxation, respectively (p less than 0.01, F-test). Requiring an SD less than or equal to 10 per cent...

  17. Relaxation process of coherent transients in the presence of an adjacent strongly driven transition

    International Nuclear Information System (INIS)

    Feng Xiaomin; Yang Lijun; Li Xiaoli; Zhang Lianshui; Han Li; Guo Qinglin; Fu Guangsheng

    2007-01-01

    Coherent transient occurs when a two-level transition is subjected to pulsed laser excitation. The relaxation process of coherent transient depends on both the longitudinal and transverse relaxation parameters of the two-level transition, which is related to the population and coherence decay rates. In this paper we study relaxation process of a new type coherent transients observed by applying a pulsed laser excitation to a two-level transition in the presence of a second strong continuous-wave (cw) coherent field coupling one of the two levels to a third level, that is, in a three-level double-resonance configuration. The relaxation process of coherent transients is studied as a function of relaxation parameters of both the two-level transition excited by the pulsed laser field and the transition coupled by the cw laser field. It is shown that by involving a third level with coherent field the relaxation process of coherent transients of a two-level transition can be modified. Our study illustrates a new way of controlling relaxation process of coherent transients in a two-level transition by a second coherent laser and this has important implication for quantum information storage and quantum computing

  18. Dual resonance approach to optical signal processing beyond the carrier relaxation rate

    DEFF Research Database (Denmark)

    Heuck, Mikkel; Kristensen, Philip Trøst; Mørk, Jesper

    2014-01-01

    We propose using two optical cavities in a differential control scheme to increase the bandwidth of cavity-based semiconductor optical signal processing devices beyond the limit given by the slowest carrier relaxation rate of the medium.......We propose using two optical cavities in a differential control scheme to increase the bandwidth of cavity-based semiconductor optical signal processing devices beyond the limit given by the slowest carrier relaxation rate of the medium....

  19. CdZnTe quantum dots study: energy and phase relaxation process

    International Nuclear Information System (INIS)

    Viale, Yannick

    2004-01-01

    We present a study of the electron-hole pair energy and phase relaxation processes in a CdTe/ZnTe heterostructure, in which quantum dots are embedded. CdZnTe quantum wells with a high Zinc concentration, separated by ZnTe barriers, contain islands with a high cadmium concentration. In photoluminescence excitation spectroscopy experiments, we evidence two types of electron hole pair relaxation processes. After being excited in the CdZnTe quantum well, the pairs relax their energy by emitting a cascade of longitudinal optical phonons until they are trapped in the quantum dots. Before their radiative recombination follows an intra-dot relaxation, which is attributed to a lattice polarization mechanism of the quantum dots. It is related to the coupling between the electronic and the vibrational states. Both relaxation mechanisms are reinforced by the strong polar character of the chemical bond in II-VI compounds. Time resolved measurements of transmission variations in a pump-probe configuration allowed us to investigate the population dynamics of the electron-hole pairs during the relaxation process. We observe a relaxation time of about 2 ps for the longitudinal phonon emission cascade in the quantum well before a saturation of the quantum dot transition. We also measured an intra-box relaxation time of 25 ps. The comparison of various cascades allows us to estimate the emission time of a longitudinal optical phonon in the quantum well to be about 100 fs. In four waves mixing experiments, we observe oscillations that we attribute to quantum beats between excitonic and bi-excitonic transitions. The dephasing times that we measure as function of the density of photons shows that excitons are strongly localized in the quantum dots. The excitonic dephasing time is much shorter than the radiative lifetime and is thus controlled by the intra-dot relaxation time. (author) [fr

  20. 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

  1. 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.

  2. Intra-well relaxation process in magnetic fluids subjected to strong polarising fields

    Energy Technology Data Exchange (ETDEWEB)

    Marin, C.N., E-mail: cmarin@physics.uvt.ro [West University of Timisoara, Faculty of Physics, B-dul V. Parvan, No. 4, Timisoara 300223 (Romania); Fannin, P.C. [Department of Electronic and Electrical Engineering, Trinity College, Dublin 2 (Ireland); Malaescu, I.; Barvinschi, P.; Ercuta, A. [West University of Timisoara, Faculty of Physics, B-dul V. Parvan, No. 4, Timisoara 300223 (Romania)

    2012-02-15

    We report on the frequency and field dependent complex magnetic susceptibility measurements of a kerosene-based magnetic fluid with iron oxide nanoparticles, stabilized with oleic acid, in the frequency range 0.1-6 GHz and over the polarising field range of 0-168.4 kA/m. By increasing polarising field, H, a subsidiary loss-peak clearly occurs in the vicinity of the ferromagnetic resonance peak, from which it remains distinct even in strong polarising fields of 168.4 kA/m. This is in contrast to other reported cases in which the intra-well relaxation process is manifested only as a shoulder of the resonance peak, which vanishes in polarising fields larger than that of 100 kA/m. The results of the XRD analysis connected to the anisotropy field results confirm that the investigated sample contains particles of magnetite and of the tetragonal phase of maghemite. Taking into account the characteristics of our sample, the theoretical analysis revealed that the intra-well relaxation process of the small particles of the tetragonal phase of maghemite may be responsible for the subsidiary loss peak of the investigated magnetic fluid. - Highlights: > Intra-well relaxation process in a magnetic fluid is studied. > Sample consists of the tetragonal phase of maghemite and magnetite particles. > A subsidiary relaxation peak is observed in the vicinity of the resonance peak. > Relaxation peak is correlated to the intra-well relaxation process. > It is assigned to the tetragonal phase of maghemite particles.

  3. Direct simulation Monte Carlo modeling of relaxation processes in polyatomic gases

    Science.gov (United States)

    Pfeiffer, M.; Nizenkov, P.; Mirza, A.; Fasoulas, S.

    2016-02-01

    Relaxation processes of polyatomic molecules are modeled and implemented in an in-house Direct Simulation Monte Carlo code in order to enable the simulation of atmospheric entry maneuvers at Mars and Saturn's Titan. The description of rotational and vibrational relaxation processes is derived from basic quantum-mechanics using a rigid rotator and a simple harmonic oscillator, respectively. Strategies regarding the vibrational relaxation process are investigated, where good agreement for the relaxation time according to the Landau-Teller expression is found for both methods, the established prohibiting double relaxation method and the new proposed multi-mode relaxation. Differences and applications areas of these two methods are discussed. Consequently, two numerical methods used for sampling of energy values from multi-dimensional distribution functions are compared. The proposed random-walk Metropolis algorithm enables the efficient treatment of multiple vibrational modes within a time step with reasonable computational effort. The implemented model is verified and validated by means of simple reservoir simulations and the comparison to experimental measurements of a hypersonic, carbon-dioxide flow around a flat-faced cylinder.

  4. Direct simulation Monte Carlo modeling of relaxation processes in polyatomic gases

    International Nuclear Information System (INIS)

    Pfeiffer, M.; Nizenkov, P.; Mirza, A.; Fasoulas, S.

    2016-01-01

    Relaxation processes of polyatomic molecules are modeled and implemented in an in-house Direct Simulation Monte Carlo code in order to enable the simulation of atmospheric entry maneuvers at Mars and Saturn’s Titan. The description of rotational and vibrational relaxation processes is derived from basic quantum-mechanics using a rigid rotator and a simple harmonic oscillator, respectively. Strategies regarding the vibrational relaxation process are investigated, where good agreement for the relaxation time according to the Landau-Teller expression is found for both methods, the established prohibiting double relaxation method and the new proposed multi-mode relaxation. Differences and applications areas of these two methods are discussed. Consequently, two numerical methods used for sampling of energy values from multi-dimensional distribution functions are compared. The proposed random-walk Metropolis algorithm enables the efficient treatment of multiple vibrational modes within a time step with reasonable computational effort. The implemented model is verified and validated by means of simple reservoir simulations and the comparison to experimental measurements of a hypersonic, carbon-dioxide flow around a flat-faced cylinder

  5. Direct simulation Monte Carlo modeling of relaxation processes in polyatomic gases

    Energy Technology Data Exchange (ETDEWEB)

    Pfeiffer, M., E-mail: mpfeiffer@irs.uni-stuttgart.de; Nizenkov, P., E-mail: nizenkov@irs.uni-stuttgart.de; Mirza, A., E-mail: mirza@irs.uni-stuttgart.de; Fasoulas, S., E-mail: fasoulas@irs.uni-stuttgart.de [Institute of Space Systems, University of Stuttgart, Pfaffenwaldring 29, D-70569 Stuttgart (Germany)

    2016-02-15

    Relaxation processes of polyatomic molecules are modeled and implemented in an in-house Direct Simulation Monte Carlo code in order to enable the simulation of atmospheric entry maneuvers at Mars and Saturn’s Titan. The description of rotational and vibrational relaxation processes is derived from basic quantum-mechanics using a rigid rotator and a simple harmonic oscillator, respectively. Strategies regarding the vibrational relaxation process are investigated, where good agreement for the relaxation time according to the Landau-Teller expression is found for both methods, the established prohibiting double relaxation method and the new proposed multi-mode relaxation. Differences and applications areas of these two methods are discussed. Consequently, two numerical methods used for sampling of energy values from multi-dimensional distribution functions are compared. The proposed random-walk Metropolis algorithm enables the efficient treatment of multiple vibrational modes within a time step with reasonable computational effort. The implemented model is verified and validated by means of simple reservoir simulations and the comparison to experimental measurements of a hypersonic, carbon-dioxide flow around a flat-faced cylinder.

  6. Analysis of the kinetics of the fragile fracture process in Mo monocrystals in quasi-relaxation

    International Nuclear Information System (INIS)

    Tamayo Meza, Pedro; Bautista Godinez, Eric Gustavo; Yermishkin, Viacheslav

    2008-01-01

    The method of quasi-relaxation, generally known as the force relaxation method, has been widely applied in the study of elementary dislocational processes. It is essential for the study and analysis of thermoactivated mechanisms, for the determination of the energy of interaction between dislocations and inclusions, in the definition of the dislocational constants, to predict the development of creep, and even for the study of fracture kinetics. For the first time the use of the quasi-relaxation method for evaluating the fragile fracture tendency was presented in the work. However, as usually carried out, the use of mass specimens and the development of a considerable plastic deformation in the vertex of the crack-notch sample limits the possibilities for this method. Many studies analyze the theoretical aspects of the fracture process, and the obtention of reliable quantitative information about the behavior of the dislocation based on an analytical description of the process, and how and when it influences the conditions under which the final catastrophic fracture occurs. This work proposes a new method to analyze the effect of a tension concentrator on the surface of Mo monocrystal specimens. The relaxation of the force and the increase in the crack opening is related to the development of the plastic zone in its vertex with the help of the Irwin correction. During the relaxation, the crack-groove grows until it attains the length of the plastic zone. Specimens with and without force concentrators were tested in quasi-relaxation. The cracks appearing under these conditions are analyzed using a scanning electron microscopy (SEM). The crack appearing in the specimens under load conditions, whose development produced heavy force relaxation, allowed the force relaxation value to be defined and compared in the specimens with and without tension concentrators (au)

  7. Viscoelastic characterization of compacted pharmaceutical excipient materials by analysis of frequency-dependent mechanical relaxation processes

    Science.gov (United States)

    Welch, K.; Mousavi, S.; Lundberg, B.; Strømme, M.

    2005-09-01

    A newly developed method for determining the frequency-dependent complex Young's modulus was employed to analyze the mechanical response of compacted microcrystalline cellulose, sorbitol, ethyl cellulose and starch for frequencies up to 20 kHz. A Debye-like relaxation was observed in all the studied pharmaceutical excipient materials and a comparison with corresponding dielectric spectroscopy data was made. The location in frequency of the relaxation peak was shown to correlate to the measured tensile strength of the tablets, and the relaxation was interpreted as the vibrational response of the interparticle hydrogen and van der Waals bindings in the tablets. Further, the measured relaxation strength, holding information about the energy loss involved in the relaxation processes, showed that the weakest material in terms of tensile strength, starch, is the material among the four tested ones that is able to absorb the most energy within its structure when exposed to external perturbations inducing vibrations in the studied frequency range. The results indicate that mechanical relaxation analysis performed over relatively broad frequency ranges should be useful for predicting material properties of importance for the functionality of a material in applications such as, e.g., drug delivery, drug storage and handling, and also for clarifying the origin of hitherto unexplained molecular processes.

  8. Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene

    Science.gov (United States)

    Hao, Qiaoli; Deng, Xulan; Long, Jinyou; Wang, Yanmei; Abulimiti, Bumaliya; Zhang, Bing

    2017-08-01

    Ultrafast electronic relaxation processes following two photoexcitation of 400 nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of 85 ± 10 fs and 2.4 ± 0.3 ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

  9. Atomistic simulation of processes in Ni-base alloys with account for local relaxations

    International Nuclear Information System (INIS)

    Bursik, Jiri

    2007-01-01

    Ordering in Ni-base superalloys is the crucial process controlling the development of the characteristic two-phase microstructure and subsequently the mechanical properties. Systems containing up to six alloying elements typical of advanced Ni-based superalloys are modelled in this work using a Monte Carlo approach with phenomenological Lennard-Jones pair potentials and interactions up to the third coordination sphere. Three-dimensional crystal block is used with over 10 5 atoms. Molecular dynamics approach is used to relax local atomic positions in course of ordering processes under applied stress. The importance of taking into account both relaxation of modelled block dimensions and relaxation of local atomic positions is discussed

  10. Relaxation processes in a lower disorder order transition diblock copolymer

    International Nuclear Information System (INIS)

    Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora; Hernández, Rebeca; Sprung, Michael

    2015-01-01

    The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T ODT , the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system

  11. Decay of Metastable State with Account of Agglomeration and Relaxation Processes

    Directory of Open Access Journals (Sweden)

    Victor Kurasov

    2016-01-01

    Full Text Available Theoretical description of the metastable phase decay kinetics in the presence of specific connections between the embryos of small sizes has been given. The theory of the decay kinetics in the presence of relaxation processes is constructed in analytical manner. The m-mers nucleation is investigated and the global kinetics of decay is also constructed in this case analytically.

  12. Non-equilibrium reacting gas flows kinetic theory of transport and relaxation processes

    CERN Document Server

    Nagnibeda, Ekaterina; Nagnibeda, Ekaterina

    2009-01-01

    This volume develops the kinetic theory of transport phenomena and relaxation processes in the flows of reacting gas mixtures. The theory is applied to the modeling of non-equilibrium flows behind strong shock waves, in the boundary layer, and in nozzles.

  13. Relaxation of the electron spin in quantum dots via one- and two-phonon processes

    International Nuclear Information System (INIS)

    Calero, C.; Chudnovsky, E.M.; Garanin, D.A.

    2007-01-01

    We have studied direct and Raman processes of the decay of electron spin states in a quantum dot via radiation of phonons corresponding to elastic twists. Universal dependence of the spin relaxation rate on the strength and direction of the magnetic field has been obtained in terms of the electron gyromagnetic tensor and macroscopic elastic constants of the solid

  14. Relaxation of the electron spin in quantum dots via one- and two-phonon processes

    Energy Technology Data Exchange (ETDEWEB)

    Calero, C. [Department of Physics and Astronomy, Lehman College, City University of New York, 250 Bedford Park Boulevard West, Bronx, NY 10468-1589 (United States)]. E-mail: carlos.calero-borrallo@lehman.cuny.edu; Chudnovsky, E.M. [Department of Physics and Astronomy, Lehman College, City University of New York, 250 Bedford Park Boulevard West, Bronx, NY 10468-1589 (United States); Garanin, D.A. [Department of Physics and Astronomy, Lehman College, City University of New York, 250 Bedford Park Boulevard West, Bronx, NY 10468-1589 (United States)

    2007-09-15

    We have studied direct and Raman processes of the decay of electron spin states in a quantum dot via radiation of phonons corresponding to elastic twists. Universal dependence of the spin relaxation rate on the strength and direction of the magnetic field has been obtained in terms of the electron gyromagnetic tensor and macroscopic elastic constants of the solid.

  15. 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.

  16. The modified relaxation time function: A novel analysis technique for relaxation processes. Application to high-temperature molybdenum internal friction peaks

    International Nuclear Information System (INIS)

    Matteo, C.L.; Lambri, O.A.; Zelada-Lambri, G.I.; Sorichetti, P.A.; Garcia, J.A.

    2008-01-01

    The modified relaxation time (MRT) function, which is based on a general linear viscoelastic formalism, has several important mathematical properties that greatly simplify the analysis of relaxation processes. In this work, the MRT is applied to the study of the relaxation damping peaks in deformed molybdenum at high temperatures. The dependence of experimental data from these relaxation processes with temperature are adequately described by a Havriliak-Negami (HN) function, and the MRT makes it possible to find a relation between the parameters of the HN function and the activation energy of the process. The analysis reveals that for the relaxation peak appearing at temperatures below 900 K, the physical mechanism is related to a vacancy-diffusion-controlled movement of dislocations. In contrast, when the peak appears at temperatures higher than 900 K, the damping is controlled by a mechanism of diffusion in the low-temperature tail of the peak, and in the high-temperature tail of the peak the creation plus diffusion of vacancies at the dislocation line occurs

  17. 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).

  18. Experimental evidence for simultaneous relaxation processes in super spin glass γ-Fe2O3 nanoparticle system

    Science.gov (United States)

    Nikolic, V.; Perovic, M.; Kusigerski, V.; Boskovic, M.; Mrakovic, A.; Blanusa, J.; Spasojevic, V.

    2015-03-01

    Spherical γ-Fe2O3 nanoparticles with the narrow size distribution of (5 ± 1) nm were synthesized by the method of thermal decomposition from iron acetyl acetonate precursor. The existence of super spin-glass state at low temperatures and in low applied magnetic fields was confirmed by DC magnetization measurements on a SQUID magnetometer. The comprehensive investigation of magnetic relaxation dynamics in low-temperature region was conducted through the measurements of single-stop and multiple stop ZFC memory effects, ZFC magnetization relaxation, and AC susceptibility measurements. The experimental findings revealed the peculiar change of magnetic relaxation dynamics at T ≈ 10 K, which arose as a consequence of simultaneous existence of different relaxation processes in Fe2O3 nanoparticle system. Complementarity of the applied measurements was utilized in order to single out distinct relaxation processes as well as to elucidate complex relaxation mechanisms in the investigated interacting nanoparticle system.

  19. Relaxation processes in optically excites metal clusters; Relaxationsprozesse in optisch angeregten Metallclustern

    Energy Technology Data Exchange (ETDEWEB)

    Stanzel, J.

    2007-08-10

    The present work is concerned with the dynamics of optically excited metal clusters in the gas phase. Small mass-selected gold and tungsten cluster anions (Au{sup -}{sub n}, n=5-8, 14, 20 and W{sup -}{sub n}, n=3-14) are studied using femtosecond time-resolved photoelectron spectroscopy. Depending on the electronic structure in the valence region as well as on the optical excitation energy fundamentally different relaxation processes are observed. In small gold cluster anions excited with 1.56 eV an isolated electronically excited state is populated. The time-dependent measurements are strongly sizedependent and open insights into photoinduced geometry changes of the nuclear framework. Oscillatory vibrational wavepacket motion in Au{sup -}{sub 5}, an extremely longlived ({tau} >90 ns) electronically excited state in Au{sup -}{sub 6} as well as photoinduced melting in Au{sup -}{sub 7} and Au{sup -}{sub 8} is monitored in real time. By increasing the OPTICAL excitation energy to 3.12 eV a completely different scenario is observed. A multitude of electronically excited states can be reached upon optical excitation and as a consequence electronic relaxation processes that take place on a time scale of 1 ps are dominating. This is shown for Au{sup -}{sub 7}, Au{sup -}{sub 14} and Au{sup -}{sub 20}. Compared to gold clusters, tungsten clusters are characterized by a significantly higher electronic density of states in the valence region. Therefore electronic relaxation processes are much more likely and take place on a significantly faster time scale. The fast electronic relaxation processes are distinguished from pure vibrational relaxation. It is shown that already in the four atomic tungsten cluster W{sup -}{sub 4} electronic relaxation processes take place on a time scale of 30 fs. In all investigated tungsten cluster anions (W{sup -}{sub n}, n=3-14) an equilibrium between electronic and vibrational system is reached within around 1 ps after optical excitation which

  20. 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.

  1. Influence of relaxation processes on the structure of a thermal boundary layer in partially ionized argon

    International Nuclear Information System (INIS)

    Dongen, M.E.H. van; Eck, R.B. van P. van; Hagebeuk, H.J.L.; Hirschberg, A.; Hutten-Mansfeld, A.C.B.; Jager, H.J.; Willems, J.F.H.

    1981-01-01

    A model for the unsteady thermal boundary-layer development at the end wall of a shock tube, in partially ionized atmospheric argon, is proposed. Consideration is given to ionization and thermal relaxation processes. In order to obtain some insight into the influence of the relaxation processes on the structure of the boundary layer, a study of the frozen and equilibrium limits has been carried out. The transition from a near-equilibrium situation in the outer part of the boundary layer towards a frozen situation near the wall is determined numerically. Experimental data on the electron and atom density profiles obtained from laser schlieren and absorption measurements are presented. A quantitative agreement between theory and experiment is found for a moderate degree of ionization (3%). At a higher degree of ionization the structure of the boundary layer is dominated by the influence of radiation cooling, which has been neglected in the model. (author)

  2. Non-rigid ultrasound image registration using generalized relaxation labeling process

    Science.gov (United States)

    Lee, Jong-Ha; Seong, Yeong Kyeong; Park, MoonHo; Woo, Kyoung-Gu; Ku, Jeonghun; Park, Hee-Jun

    2013-03-01

    This research proposes a novel non-rigid registration method for ultrasound images. The most predominant anatomical features in medical images are tissue boundaries, which appear as edges. In ultrasound images, however, other features can be identified as well due to the specular reflections that appear as bright lines superimposed on the ideal edge location. In this work, an image's local phase information (via the frequency domain) is used to find the ideal edge location. The generalized relaxation labeling process is then formulated to align the feature points extracted from the ideal edge location. In this work, the original relaxation labeling method was generalized by taking n compatibility coefficient values to improve non-rigid registration performance. This contextual information combined with a relaxation labeling process is used to search for a correspondence. Then the transformation is calculated by the thin plate spline (TPS) model. These two processes are iterated until the optimal correspondence and transformation are found. We have tested our proposed method and the state-of-the-art algorithms with synthetic data and bladder ultrasound images of in vivo human subjects. Experiments show that the proposed method improves registration performance significantly, as compared to other state-of-the-art non-rigid registration algorithms.

  3. Glass transition and relaxation processes of polymers studied by positron annihilation

    Energy Technology Data Exchange (ETDEWEB)

    Uedono, Akira; Tanigawa, Shoichiro [Tsukuba Univ., Ibaraki (Japan). Inst. of Materials Science

    1996-10-01

    The glass transition and relaxation processes of polymers were studied by the positron annihilation technique. A positron implanted into polymers might annihilate from positronium (Ps) states in open spaces. Ps is a bound state between a positron and an electron, and its nonrelativistic quantum mechanics is practically identical to that of a hydrogen atom. The lifetime of Ps can be associated with the size of the open spaces, and the formation probability of Ps provides information of motions of molecules. Since the glass transition or relaxation processes affect behavior of open spaces, one can study these phenomena through the detection of the open spaces using the positron annihilation technique. In the present paper, we report studies of the glass transition and relaxation processes in polyethylene, polypropylene, and polystyrene by measurements of lifetime spectra of positrons and those of Doppler broadening profiles of the annihilation radiation. For these specimens, by measurements of the lifetime of Ps, {tau}{sub 3}, as a function of temperature, the glass transition temperature, T{sub g}, was determined as an onset temperature of the increase in the temperature coefficient of {tau}{sub 3}. Below T{sub g}, local motions of molecules were detected by measurements of the formation probability of Ps. The positron annihilation as a tool for the characterization of polymers was discussed. (author). 51 refs.

  4. Depolarization current relaxation process of insulating dielectrics after corona poling under different charging conditions

    Directory of Open Access Journals (Sweden)

    J. W. Zhang

    2017-10-01

    Full Text Available As an insulating dielectric, polyimide is favorable for the application of optoelectronics, electrical insulation system in electric power industry, insulating, and packaging materials in space aircraft, due to its excellent thermal, mechanical and electrical insulating stability. The charge storage profile of such insulating dielectric is utmost important to its application, when it is exposed to electron irradiation, high voltage corona discharge or other treatments. These treatments could induce changes in physical and chemical properties of treated samples. To investigate the charge storage mechanism of the insulating dielectrics after high-voltage corona discharge, the relaxation processes responsible for corona charged polyimide films under different poling conditions were analyzed by the Thermally Stimulated Discharge Currents method (TSDC. In the results of thermal relaxation process, the appearance of various peaks in TSDC spectra provided a deep insight into the molecular status in the dielectric material and reflected stored space charge relaxation process in the insulating polymers after corona discharge treatments. Furthermore, the different space charge distribution status under various poling temperature and different discharge voltage level were also investigated, which could partly reflect the influence of the ambiance condition on the functional dielectrics after corona poling.

  5. Depolarization current relaxation process of insulating dielectrics after corona poling under different charging conditions

    Science.gov (United States)

    Zhang, J. W.; Zhou, T. C.; Wang, J. X.; Yang, X. F.; Zhu, F.; Tian, L. M.; Liu, R. T.

    2017-10-01

    As an insulating dielectric, polyimide is favorable for the application of optoelectronics, electrical insulation system in electric power industry, insulating, and packaging materials in space aircraft, due to its excellent thermal, mechanical and electrical insulating stability. The charge storage profile of such insulating dielectric is utmost important to its application, when it is exposed to electron irradiation, high voltage corona discharge or other treatments. These treatments could induce changes in physical and chemical properties of treated samples. To investigate the charge storage mechanism of the insulating dielectrics after high-voltage corona discharge, the relaxation processes responsible for corona charged polyimide films under different poling conditions were analyzed by the Thermally Stimulated Discharge Currents method (TSDC). In the results of thermal relaxation process, the appearance of various peaks in TSDC spectra provided a deep insight into the molecular status in the dielectric material and reflected stored space charge relaxation process in the insulating polymers after corona discharge treatments. Furthermore, the different space charge distribution status under various poling temperature and different discharge voltage level were also investigated, which could partly reflect the influence of the ambiance condition on the functional dielectrics after corona poling.

  6. Growth and relaxation processes in Ge nanocrystals on free-standing Si(001) nanopillars.

    Science.gov (United States)

    Kozlowski, G; Zaumseil, P; Schubert, M A; Yamamoto, Y; Bauer, J; Schülli, T U; Tillack, B; Schroeder, T

    2012-03-23

    We study the growth and relaxation processes of Ge crystals selectively grown by chemical vapour deposition on free-standing 90 nm wide Si(001) nanopillars. Epi-Ge with thickness ranging from 4 to 80 nm was characterized by synchrotron based x-ray diffraction and transmission electron microscopy. We found that the strain in Ge nanostructures is plastically released by nucleation of misfit dislocations, leading to degrees of relaxation ranging from 50 to 100%. The growth of Ge nanocrystals follows the equilibrium crystal shape terminated by low surface energy (001) and {113} facets. Although the volumes of Ge nanocrystals are homogeneous, their shape is not uniform and the crystal quality is limited by volume defects on {111} planes. This is not the case for the Ge/Si nanostructures subjected to thermal treatment. Here, improved structure quality together with high levels of uniformity of the size and shape is observed.

  7. Characterization of relaxation processes in interacting vortex matter through a time-dependent correlation length

    International Nuclear Information System (INIS)

    Pleimling, Michel; Täuber, Uwe C

    2015-01-01

    Vortex lines in type-II superconductors display complicated relaxation processes due to the intricate competition between their mutual repulsive interactions and pinning to attractive point or extended defects. We perform extensive Monte Carlo simulations for an interacting elastic line model with either point-like or columnar pinning centers. From measurements of the space- and time-dependent height-height correlation function for lateral flux line fluctuations, we extract a characteristic correlation length that we use to investigate different non-equilibrium relaxation regimes. The specific time dependence of this correlation length for different disorder configurations displays characteristic features that provide a novel diagnostic tool to distinguish between point-like pinning centers and extended columnar defects. (paper)

  8. Uncertainty management by relaxation of conflicting constraints in production process scheduling

    Science.gov (United States)

    Dorn, Juergen; Slany, Wolfgang; Stary, Christian

    1992-01-01

    Mathematical-analytical methods as used in Operations Research approaches are often insufficient for scheduling problems. This is due to three reasons: the combinatorial complexity of the search space, conflicting objectives for production optimization, and the uncertainty in the production process. Knowledge-based techniques, especially approximate reasoning and constraint relaxation, are promising ways to overcome these problems. A case study from an industrial CIM environment, namely high-grade steel production, is presented to demonstrate how knowledge-based scheduling with the desired capabilities could work. By using fuzzy set theory, the applied knowledge representation technique covers the uncertainty inherent in the problem domain. Based on this knowledge representation, a classification of jobs according to their importance is defined which is then used for the straightforward generation of a schedule. A control strategy which comprises organizational, spatial, temporal, and chemical constraints is introduced. The strategy supports the dynamic relaxation of conflicting constraints in order to improve tentative schedules.

  9. Evaluation of multi-exponential relaxation processes: In vitro and in vivo studies

    International Nuclear Information System (INIS)

    Henriksen, O.; Thomsen, C.; Kjaer, L.; Ring, P.

    1986-01-01

    T1 and T2 relaxation values obtained at 1.5 T were measured on 12 inversion-recovery (IR) sequences and a multiple spin-echo (SE) sequence with 32 echoes. Phantom studies were carried out for different CuSO/sub 4/ solutions, using MR imaging and reference spectrometry. The correlation was excellent (r=.98, P>.01;r=1.00, P>.01). T1 and T2 values varied less than 10% in the imaging plane. Then two-compartment phantoms were examined. For T1 and T2, the ratios T1(compartment A)/T1 (compartment B)>6 ant T2(c.A)/T2(c.B) > 6 were essential for reliable estimation. Studies on the normal brain indicate a multiexponential T1 and T2 relaxation process in gray matter

  10. Relaxation and excitation electronic processes in dielectrics irradiated by ultrafast IR and VUV pulses

    International Nuclear Information System (INIS)

    Gaudin, J.

    2005-11-01

    We studied excitation and relaxation of electrons involved during interaction of visible and VUV femtosecond pulses with dielectrics. The generated population of hot electrons, having energy of few eV to few tens of eV above the bottom of the conduction band, is responsible of phenomena ranging to defect creation to optical breakdown. Owing to two techniques: photoemission and transient photoconductivity we improve the understanding of the The first photoemission experiments deal with dielectrics irradiated by 30 fs IR pulses. The photoemission spectra measured show a large population of electrons which energy rise up to 40 eV. We interpret this result in terms of a new absorption process: direct multi-photons inter-branch transitions. The 2. type of photoemission experiments are time resolved 'pump/probe' investigation. We study the relaxation of electrons excited by a VUV pulses. We used the high order harmonics (HOH) as light sources. We found surprisingly long decay time in the range of ps timescale. Last type of experiments is photoconductivity studies of diamond samples. Using HOH as light source we measure the displacement current induced by excited electrons in the conduction band. Those electrons relax mainly by impact ionisation creating secondary electrons. Hence by probing the number of electrons we were able to measure the efficiency of these relaxation processes. We observe a diminution of this efficiency when the energy of exciting photons is above 20 eV. Owing to Monte-Carlo simulation we interpret this result in terms of band structure effect. (author)

  11. Simulation study of MHD relaxation and reconnection processes in RFP plasma

    International Nuclear Information System (INIS)

    Kusano, Kanya; Kunimoto, Kaito; Suzuki, Yoshio; Tamano, Teruo; Sato, Tetsuya

    1991-01-01

    The authors have studied several nonlinear processes in RFP plasma through the use of 3D MHD simulations. In particular, they have shed light on: (1) dynamo and self-sustainment in reversed-field pinch (RFP), (2) phase locking process in MHD relaxation, and (3) the heating and acceleration in magnetic reconnection process. First, the contributions of the kink (m = 1) mode (linearly unstable) and of the m = 0 mode (driven by nonlinear coupling) to the dynamo are qualitatively evaluated using a high accuracy simulation. It is found that, if the free energy to drive kink instabilities is as small as that in the actual experimental plasma, the m = 0 modes, driven nonlinearly, play a more important role for the flux generation than the kink modes. Secondly, numerical simulations of the self-sustainment process in a RFP are performed. It is confirmed that the self-sustainment process is a coherent oscillating process composed of the MHD relaxation and the resistive diffusion processes. Toroidal phase locking process of kink modes is numerically observed in simulations of self-reversal and self-sustainment processes. It has characteristics similar to the slinky mode observed in the OHTE experiment. A detailed investigation reveals that nonlinear coupling between the most unstable two kink modes governs the entire dynamics in all kink modes and leads to the phase locking process. They find that reconnection can accelerate plasma over a local Alfven speed. This is a result of the fact that the magnetic field in the downstream area plays a similar role to de Laval nozzle. They also investigate the heating mechanisms in reconnection process. It is revealed that the viscous heating rate is as large as the joule heating rate in the reconnection process. This result implies that the viscous heating in the reconnection process is an important candidate for the mechanism to explain the RFP experiments where the ion temperatures is higher than the electron temperature

  12. The study of magnetic properties and relaxation processes in Co/Au bimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Hrubovčák, Pavol [Department of Condensed Matter Physics, P.J. Šafárik University, Park Angelinum 9, Košice (Slovakia); Zeleňáková, Adriana, E-mail: adriana.zelenakova@upjs.sk [Department of Condensed Matter Physics, P.J. Šafárik University, Park Angelinum 9, Košice (Slovakia); Zeleňák, Vladimir [Department of Inorganic Chemistry, P.J. Šafárik University, Moyzesova 11, Košice (Slovakia); Kováč, Jozef [Institute of Experimental Physics, SAS, Watsonova 41, Košice (Slovakia)

    2015-11-15

    Co/Au bimetallic fine nanoparticles were prepared employing the method of microemulsion using reverse micelle as nanoreactor, controlling the particles size. Magnetic and structural properties of two different samples Co/Au1 and Co/Au2 with almost comparable size of Co core and different size of Au layer were studied. The investigation of magnetic relaxation processes present in the particles was carried out by means of ac and dc magnetization data obtained at different temperatures and magnitudes of magnetic field. We observed the existence of superspin glass state characterized by the strong inter-particle interactions in the nanoparticle systems. In this paper, we discuss the attributes of novel superspin glass magnetic state reflected on various features (saturated FC magnetization at low temperatures, shift of the Cole–Cole arc downwards) and calculated parameters (relaxation time, critical exponent zv ∼ 10 and frequency dependent criterion p < 0.05). Comparison of the magnetic properties of two studied samples show that the thickness of diamagnetic Au shell significantly influences the magnetic interactions and change the relaxation dynamics. - Highlights: • Co/Au fine nanoparticles prepared by reverse micelle as nanoreactor, controlling the size. • Existence of superspin glass state confirmed from ac magnetic susceptibility study. • Individual particles exhibit the collective behavior below glass temperature T{sub SSG}. • Influence of diamagnetic shell on the magnetic properties of core–shell nanoparticles.

  13. Asymptotic description of two metastable processes of solidification for the case of large relaxation time

    International Nuclear Information System (INIS)

    Omel'yanov, G.A.

    1995-07-01

    The non-isothermal Cahn-Hilliard equations in the n-dimensional case (n = 2,3) are considered. The interaction length is proportional to a small parameter, and the relaxation time is proportional to a constant. The asymptotic solutions describing two metastable processes are constructed and justified. The soliton type solution describes the first stage of separation in alloy, when a set of ''superheated liquid'' appears inside the ''solid'' part. The Van der Waals type solution describes the free interface dynamics for large time. The smoothness of temperature is established for large time and the Mullins-Sekerka problem describing the free interface is derived. (author). 46 refs

  14. One and two-phonon processes of the spin-flip relaxation in quantum dots: Spin-phonon coupling mechanism

    Science.gov (United States)

    Wang, Zi-Wu; Li, Shu-Shen

    2012-07-01

    We investigate the spin-flip relaxation in quantum dots using a non-radiation transition approach based on the descriptions for the electron-phonon deformation potential and Fröhlich interaction in the Pavlov-Firsov spin-phonon Hamiltonian. We give the comparisons of the electron relaxations with and without spin-flip assisted by one and two-phonon processes. Calculations are performed for the dependence of the relaxation time on the external magnetic field, the temperature and the energy separation between the Zeeman sublevels of the ground and first-excited state. We find that the electron relaxation time of the spin-flip process is more longer by three orders of magnitudes than that of no spin-flip process.

  15. The relaxation time of processes in a FitzHugh-Nagumo neural system with time delay

    International Nuclear Information System (INIS)

    Gong Ailing; Zeng Chunhua; Wang Hua

    2011-01-01

    In this paper, we study the relaxation time (RT) of the steady-state correlation function in a FitzHugh-Nagumo neural system under the presence of multiplicative and additive white noises and time delay. The noise correlation parameter λ can produce a critical behavior in the RT as functions of the multiplicative noise intensity D, the additive noise intensity Q and the time delay τ. That is, the RT decreases as the noise intensities D and Q increase, and increases as the time delay τ increases below the critical value of λ. However, above the critical value, the RT first increases, reaches a maximum, and then decreases as D, Q and τ increase, i.e. a noise intensity D or Q and a time delay τ exist, at which the time scales of the relaxation process are at their largest. In addition, the additive noise intensity Q can also produce a critical behavior in the RT as a function of λ. The noise correlation parameter λ first increases the RT of processes, then decreases it below the critical value of Q. Above the critical value, λ increases it.

  16. Estimation of magnetic relaxation property for CVD processed YBCO-coated conductors

    International Nuclear Information System (INIS)

    Takahashi, Y.; Kiuchi, M.; Otabe, E.S.; Matsushita, T.; Shikimachi, K.; Watanabe, T.; Kashima, N.; Nagaya, S.

    2010-01-01

    Ion Beam Assist Deposition/Chemical Vapor Deposition(IBAD/CVD)-processed YBCO-coated conductors with high critical current density J c at high magnetic fields are expected to be applied to superconducting equipments such as superconducting magnetic energy storage (SMES). For application to superconducting magnet in SMES one of the most important properties for superconductors is the relaxation property of superconducting current. In this paper, the relaxation property is investigated for IBAD/CVD-processed YBCO-coated conductors of the superconducting layer in the range of 0.18-0.90 μm. This property can be quantitatively characterized by the apparent pinning potential, U 0 *. It is found that U 0 * takes a smaller value due to the two-dimensional pinning mechanism at high magnetic fields for conductor with thinner superconducting layer. Although U 0 * decreases with increasing thickness at low magnetic fields at 20 K, it increases at high magnetic fields. The results are theoretically explained by the model of the flux creep and flow based on the dimensionality of flux pinning. Scaling analysis is examined for the dependence of U 0 * on the magnetic field, temperature and the layer thickness.

  17. Understanding charge carrier relaxation processes in terbium arsenide nanoparticles using transient absorption spectroscopy

    Science.gov (United States)

    Vanderhoef, Laura R.

    Erbium arsenide nanoparticles epitaxially grown within III-V semiconductors have been shown to improve the performance of devices for applications ranging from thermoelectrics to THz pulse generation. The small size of rare-earth nanoparticles suggests that interesting electronic properties might emerge as a result of both spatial confinement and surface states. However, ErAs nanoparticles do not exhibit any signs of quantum confinement or an emergent bandgap, and these experimental observations are understood from theory. The incorporation of other rare-earth monopnictide nanoparticles into III-V hosts is a likely path to engineering carrier excitation, relaxation and transport dynamics for optoelectronic device applications. However, the electronic structure of these other rare-earth monopnictide nanoparticles remains poorly understood. The objective of this research is to explore the electronic structure and optical properties of III-V materials containing novel rare-earth monopnictides. We use ultrafast pump-probe spectroscopy to investigate the electronic structure of TbAs nanoparticles in III-V hosts. We start with TbAs:GaAs, which was expected to be similar to ErAs:GaAs. We study the dynamics of carrier relaxation into the TbAs states using optical pump terahertz probe transient absorption spectroscopy. By analyzing how the carrier relaxation rates depend on pump fluence and sample temperature, we conclude that the TbAs states are saturable. Saturable traps suggest the existence of a bandgap for TbAs nanoparticles, in sharp contrast with previous results for ErAs. We then apply the same experimental technique to two samples of TbAs nanoparticles in InGaAs with different concentrations of TbAs. We observe similar relaxation dynamics associated with trap saturation, though the ability to resolve these processes is contingent upon a high enough TbAs concentration in the sample. We have also constructed an optical pump optical probe transient absorption

  18. Influence of relaxation processes on the evaluation of the metastable defect density in Cu(In,Ga)Se{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Maciaszek, M.; Zabierowski, P. [Faculty of Physics, Warsaw University of Technology, Koszykowa 75, Warszawa 00 662 (Poland)

    2016-06-07

    In this contribution, we investigated by means of numerical simulations the influence of relaxation processes related to metastable defects on electrical characteristics of Cu(In,Ga)Se{sub 2}. In particular, we analyzed the relaxation of a metastable state induced by illumination at a fixed temperature as well as the dependence of the hole concentration on the temperature during cooling. The knowledge of these two relaxation processes is crucial in the evaluation of the hole concentration in the relaxed state and after light soaking. We have shown that the distribution of the metastable defects can be considered frozen below 200 K. The hole capture cross section was estimated as ∼3 × 10{sup −15} cm{sup 2}. It was shown that the usually used cooling rates may lead to relevant changes of the hole concentration. We calculated the lower limit of the hole concentration after cooling, and we presented how it depends on densities of shallow acceptors and metastable defects. Moreover, we proposed a method which allows for the evaluation of shallow acceptor and metastable defect densities from two capacitance-voltage profiles measured in the relaxed and light soaking states. Finally, we indicated experimental conditions in which the influence of relaxation processes on the accuracy of this method is the smallest.

  19. Diffusion processes in the relaxed cross sections for the reaction 107109Ag+20Ne

    International Nuclear Information System (INIS)

    Babinet, R.; Moretto, L.G.; Galin, J.; Jared, R.; Moulton, J.; Thompson, S.G.

    1976-01-01

    The fragments emitted in the reaction 107 109 Ag+ 20 Ne at 175 and 252 MeV bombarding energy have been identified in charge up to Z=32. Kinetic energy distributions, cross sections and angular distributions have been measured for each Z. The kinetic energy spectra show the two usual components: the quasielastic component and the relaxed component. The Z-distribution of the latter is fairly flat, slowly decreasing up to Z approximately 15 and then rising again up to Z=30. The variations in the Z-distribution are more pronounced at the lower bombarding energy. The angular distributions associated with the relaxed component are forward peaked for Z-values close to that of the projectile and behave like 1/sintheta for larger Z-values. The forward peaking is very substantial for Z 10 the forward peaking in excess of 1/sintheta disappears around Z=15. These features are interpreted in terms of a diffusion process along the asymmetry coordinate of a short-lived intermediate complex. (Auth.)

  20. In vivo measurements of relaxation process in the human liver by MRI. The role of respiratory gating/triggering

    DEFF Research Database (Denmark)

    Thomsen, C; Henriksen, O; Ring, P

    1988-01-01

    In vivo estimation of relaxation processes in the liver by magnetic resonance imaging (MRI) may be helpful for characterization of various pathological conditions in the liver. However, such measurements may be significantly hampered by movement of the liver with the respiration. The effect...... of synchronization of data acquisition to the respiratory cycle on measured T1- and T2-relaxation curves was studied in normal subjects, patients with diffuse liver disease, and patients with focal liver pathology. Multi spin echo sequences with five different repetition times were used. The measurements were...... carried out with and without respiratory gating/triggering. In the healthy subjects as well as in the patients with diffuse liver diseases respiratory synchronization did not alter the obtained relaxation curves. However, in the patients with focal pathology the relaxation curves were significantly...

  1. Vibrational-rotational relaxation of the simplest hydrogen-containing molecules (review)

    International Nuclear Information System (INIS)

    Molevich, N.E.; Oraevskii, A.N.

    1987-01-01

    In connection with the development of chemical lasers much attention is now devoted to the study of kinetic processes is gaseous mixtures containing the hydrogen halides. Vibrational relaxation of molecules if primarily studied without specifying its relation to the rational levels. Rotational relaxation is regarded a priori as faster than vibrational relaxation, so that the population of the rotational levels is assumed to be in equilibrium. This approach to the relaxation of hydrogen halide molecules (and other diatomic hydrogen-containing molecules), however, is unable to explain satisfactorily the results of the papers discussed below. An analysis of the data obtained in these papers leads to the conclusion that the general picture of relaxation in diatomic hydrogen-containing molecules must be viewed as a unified process of vibrational and rotational relaxation. It is shown that those effects observed during vibrational relaxation of such molecules which are unusual from the standpoint of the theory of vibrational-translational relaxation are well explained in terms of intermolecular vibrational-rotational relaxation together with pure rotational relaxation

  2. Rational extended thermodynamics of a rarefied polyatomic gas with molecular relaxation processes

    Science.gov (United States)

    Arima, Takashi; Ruggeri, Tommaso; Sugiyama, Masaru

    2017-10-01

    We present a more refined version of rational extended thermodynamics of rarefied polyatomic gases in which molecular rotational and vibrational relaxation processes are treated individually. In this case, we need a triple hierarchy of the moment system and the system of balance equations is closed via the maximum entropy principle. Three different types of the production terms in the system, which are suggested by a generalized BGK-type collision term in the Boltzmann equation, are adopted. In particular, the rational extended thermodynamic theory with seven independent fields (ET7) is analyzed in detail. Finally, the dispersion relation of ultrasonic wave derived from the ET7 theory is confirmed by the experimental data for CO2, Cl2, and Br2 gases.

  3. Investigation of transitions and relaxation processes in polystyrene by using positron annihilation

    International Nuclear Information System (INIS)

    Ban, M.; Kyoto, M.

    1996-01-01

    The glass transition and relaxation processes in polystyrene resins with the number average molecular weight ranging from 7.0 x 10 2 to 9.8 x 10 4 were studied with the positron annihilation technique. The pick-off annihilation lifetime of ortho-positronium (τ 3 ) and its intensity (Ι 3 ) were measured in the temperature range from 20 to 430 K. The glass transition temperature (Τ g ) was determined as an onset temperature coefficient of τ 3 x Τ g shows the molecular weight dependence in these samples. Below Τ g , local motions were detected by measurements of Ι 3 . The local motions could be observed above 100 K in this experiment. Ι 3 show the minimum at around 250 K and it does not show molecular weight dependence. (author)

  4. Investigations of effect of phase change mass transfer rate on cavitation process with homogeneous relaxation model

    Energy Technology Data Exchange (ETDEWEB)

    He, Zhixia; Zhang, Liang; Saha, Kaushik; Som, Sibendu; Duan, Lian; Wang, Qian

    2017-12-01

    The super high fuel injection pressure and micro size of nozzle orifice has been an important development trend for the fuel injection system. Accordingly, cavitation transient process, fuel compressibility, amount of noncondensable gas in the fuel and cavitation erosion have attracted more attention. Based on the fact of cavitation in itself is a kind of thermodynamic phase change process, this paper takes the perspective of the cavitation phase change mass transfer process to analyze above mentioned phenomenon. The two-phase cavitating turbulent flow simulations with VOF approach coupled with HRM cavitation model and U-RANS of standard k-ε turbulence model were performed for investigations of cavitation phase change mass transfer process. It is concluded the mass transfer time scale coefficient in the Homogenous Relaxation Model (HRM) representing mass transfer rate should tend to be as small as possible in a condition that ensured the solver stable. At very fast mass transfer rate, the phase change occurs at very thin interface between liquid and vapor phase and condensation occurs more focused and then will contribute predictably to a more serious cavitation erosion. Both the initial non-condensable gas in fuel and the fuel compressibility can accelerate the cavitation mass transfer process.

  5. Anomalous relaxation and self-organization in non-equilibrium processes

    OpenAIRE

    Fatkullin, Ibrahim; Kladko, Konstantin; Mitkov, Igor; Bishop, A. R.

    2000-01-01

    We study thermal relaxation in ordered arrays of coupled nonlinear elements with external driving. We find, that our model exhibits dynamic self-organization manifested in a universal stretched-exponential form of relaxation. We identify two types of self-organization, cooperative and anti-cooperative, which lead to fast and slow relaxation, respectively. We give a qualitative explanation for the behavior of the stretched exponent in different parameter ranges. We emphasize that this is a sys...

  6. Relaxation System

    Science.gov (United States)

    1987-01-01

    Environ Corporation's relaxation system is built around a body lounge, a kind of super easy chair that incorporates sensory devices. Computer controlled enclosure provides filtered ionized air to create a feeling of invigoration, enhanced by mood changing aromas. Occupant is also surrounded by multidimensional audio and the lighting is programmed to change colors, patterns, and intensity periodically. These and other sensory stimulators are designed to provide an environment in which the learning process is stimulated, because research has proven that while an individual is in a deep state of relaxation, the mind is more receptive to new information.

  7. Relaxation of Isolated Ventricular Cardiomyocytes by a Voltage-Dependent Process

    Science.gov (United States)

    Bridge, John H. B.; Spitzer, Kenneth W.; Ershler, Philip R.

    1988-08-01

    Cell contraction and relaxation were measured in single voltage-clamped guinea pig cardiomyocytes to investigate the contribution of sarcolemmal Na+-Ca2+ exchange to mechanical relaxation. Cells clamped from -80 to 0 millivolts displayed initial phasic and subsequent tonic contractions; caffeine reduced or abolished the phasic and enlarged the tonic contraction. The rate of relaxation from tonic contractions was steeply voltage-dependent and was significantly slowed in the absence of a sarcolemmal Na+ gradient. Tonic contractions elicited in the absence of a Na+ gradient promptly relaxed when external Na+ was applied, reflecting activation of Na+-Ca2+ exchange. It appears that a voltage-dependent Na+-Ca2+ exchange can rapidly mechanically relax mammalian heart muscle.

  8. Multiple relaxation processes in high-energy ion irradiated kapton-H polyimide: Thermally stimulated depolarization current study

    International Nuclear Information System (INIS)

    Garg, Maneesha; Quamara, J.K.

    2006-01-01

    High-energy ion irradiation effects on the thermally stimulated depolarization current (Tdc) behaviour of kapton-H samples (12.5 μm) irradiated with 50 MeV Li ion (fluence 5 x 10 4 , 10 5 and 5 x 10 5 ions/cm 2 ) have been investigated. The TSDC spectra of the irradiated samples reveal that the β-peak (appearing around 80-110 deg. C) associated with dipolar relaxation has been significantly affected owing to the demerization of carbonyl groups due to irradiation. The TSDC spectra also reveal a new relaxation process (termed as γ-relaxation) around 30 deg. C, due to increased water absorptivity in irradiated samples. The peak around 200 deg. C (α-peak) associated with space charge relaxation process also shows a behavioural change with ion irradiation. The peak not only shifts towards the higher temperature with increasing fluence but also show an increase in its activation energy (0.33-0.99 eV) with increasing polarizing field. The creation of new deep energy trap centers due to the formation of conjugated bonds after irradiation is responsible for this modification. The Cole-Cole distribution curves show the formation of new sub-polar group with different characteristic relaxation time

  9. 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.)

  10. Dynamic relaxation processes in compressible multiphase flows. Application to evaporation phenomena

    Directory of Open Access Journals (Sweden)

    Le Métayer O.

    2013-07-01

    Full Text Available Phase changes and heat exchanges are examples of physical processes appearing in many industrial applications involving multiphase compressible flows. Their knowledge is of fundamental importance to reproduce correctly the resulting effects in simulation tools. A fine description of the flow topology is thus required to obtain the interfacial area between phases. This one is responsible for the dynamics and the kinetics of heat and mass transfer when evaporation or condensation occurs. Unfortunately this exchange area cannot be obtained easily and accurately especially when complex mixtures (drops, bubbles, pockets of very different sizes appear inside the transient medium. The natural way to solve this specific trouble consists in using a thin grid to capture interfaces at all spatial scales. But this possibility needs huge computing resources and can be hardly used when considering physical systems of large dimensions. A realistic method is to consider instantaneous exchanges between phases by the way of additional source terms in a full non-equilibrium multiphase flow model [2,15,17]. In this one each phase obeys its own equation of state and has its own set of equations and variables (pressure, temperature, velocity, energy, entropy,.... When enabling the relaxation source terms the multiphase mixture instantaneously tends towards a mechanical or thermodynamic equilibrium state at each point of the flow. This strategy allows to mark the boundaries of the real flow behavior and to magnify the dominant physical effects (heat exchanges, evaporation, drag,... inside the medium. A description of the various relaxation processes is given in the paper. Les changements de phase et les transferts de chaleur sont des exemples de phénomènes physiques présents dans de nombreuses applications industrielles faisant intervenir des écoulements compressibles multiphasiques. La connaissance des mécanismes associés est primordiale afin de reproduire

  11. Dual-resonances approach to broadband cavity-assisted optical signal processing beyond the carrier relaxation rate

    DEFF Research Database (Denmark)

    Heuck, Mikkel; Kristensen, Philip Trøst; Mørk, Jesper

    2014-01-01

    We propose and analyze a differential control scheme for cavity-enhanced optical signal processing devices based on carrier nonlinearities. The scheme relies on two optical cavities to increase the bandwidth beyond the limit given by the slowest carrier relaxation rate of the medium. Practical...

  12. Anisotropy and relaxation processes of uniaxially oriented CoFe2O4 nanoparticles dispersed in PDMS

    International Nuclear Information System (INIS)

    Antonel, P.S.; Negri, R.M.; Leyva, A.G.; Jorge, G.A.

    2012-01-01

    When a uniaxial magnetic field is applied to a non-magnetic dispersive medium filled with magnetic nanoparticles, they auto-assemble into thin needles parallel to the field direction, due to the strong dipolar interaction among them. We have prepared in this way magnetically oriented nanocomposites of nanometer-size CoFe 2 O 4 particles in a polydimethylsiloxane polymer matrix, with 10% w/w of magnetic particles. We present the characteristic magnetic relaxation curves measured after the application of a magnetic field forming an angle α with respect to the needle direction. We show that the magnetic viscosity (calculated from the logarithmic relaxation curves) as a function of α presents a minimum at α=0, indicating slower relaxation processes associated with this configuration of fields. The results seems to point out that the local magnetic anisotropy of the nanoparticles is oriented along the needles, resulting in the macroscopic magnetic anisotropy observed in our measurements.

  13. Anisotropy and relaxation processes of uniaxially oriented CoFe{sub 2}O{sub 4} nanoparticles dispersed in PDMS

    Energy Technology Data Exchange (ETDEWEB)

    Antonel, P.S.; Negri, R.M. [Instituto de Quimica Fisica de Materiales, Ambiente y Energia (INQUIMAE), Departamento de Quimica Inorganica, Analitica y Quimica Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellon II, Av. Cantilo s/n (1428), Buenos Aires (Argentina); Leyva, A.G. [Grupo de Materia Condensada, Gerencia de Investigacion y Aplicaciones, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica, Avda. Gral. Paz 1499 (1650) San Martin, Pcia. de Buenos Aires, Argentina - Escuela de Ciencia y Tecnologia, UNSAM (Argentina); Jorge, G.A., E-mail: gjorge@df.uba.ar [Departamento de Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellon I, Av. Cantilo s/n (1428), Buenos Aires (Argentina)

    2012-08-15

    When a uniaxial magnetic field is applied to a non-magnetic dispersive medium filled with magnetic nanoparticles, they auto-assemble into thin needles parallel to the field direction, due to the strong dipolar interaction among them. We have prepared in this way magnetically oriented nanocomposites of nanometer-size CoFe{sub 2}O{sub 4} particles in a polydimethylsiloxane polymer matrix, with 10% w/w of magnetic particles. We present the characteristic magnetic relaxation curves measured after the application of a magnetic field forming an angle {alpha} with respect to the needle direction. We show that the magnetic viscosity (calculated from the logarithmic relaxation curves) as a function of {alpha} presents a minimum at {alpha}=0, indicating slower relaxation processes associated with this configuration of fields. The results seems to point out that the local magnetic anisotropy of the nanoparticles is oriented along the needles, resulting in the macroscopic magnetic anisotropy observed in our measurements.

  14. 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

  15. 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.

  16. Relaxation of the lower frit loading constraint for DWPF process control

    International Nuclear Information System (INIS)

    Brown, K.G.

    2000-01-01

    The lower limit on the frit loading parameter when measurement uncertainty is introduced has impacted DWPF performance during immobilization of Tank 42 Sludge; therefore, any defensible relaxation or omission of this constraint should correspondingly increase DWPF waste loading and efficiency. Waste loading should be increased because the addition of frit is the current remedy for exceeding the lower frit loading constraint. For example, frit was added to DWPF SME Batches 94, 97 and 98 to remedy these batches for low frit loading. Attempts were also made to add frit in addition to the optimum computed to assure the lower frit loading constraint would be satisfied; however, approximately half of the SME Batches produced after Batch 98 have violated the lower frit loading constraint. If the DWPF batches did not have to be remediated and additional frit added because of the lower frit loading limit, then both, the performance of the DWPF process and the waste loading in the glass produced would be increased. Before determining whether or not the lower frit loading limit can be relaxed or omitted, the origin of this and the other constraints related to durability prediction must be examined. The lower limit loading constraint results from the need to make highly durable glass in DWPF. It is required that DWPF demonstrate that the glass produced would have durability that is at least two standard deviations greater than that of the Environmental Assessment (EA) glass. Glass durability cannot be measured in situ, it must be predicted from composition which can be measured. Fortunately, the leaching characteristics of homogeneous waste glasses is strongly related to the total molar free energy of the constituent species. Thus the waste acceptance specification has been translated into a requirement that the total molar free energy associated with the glass composition that would be produced from a DWPF melter feed batch be less than that of the EA glass accounting for

  17. Cellular Particle Dynamics simulation of biomechanical relaxation processes of multi-cellular systems

    Science.gov (United States)

    McCune, Matthew; Kosztin, Ioan

    2013-03-01

    Cellular Particle Dynamics (CPD) is a theoretical-computational-experimental framework for describing and predicting the time evolution of biomechanical relaxation processes of multi-cellular systems, such as fusion, sorting and compression. In CPD, cells are modeled as an ensemble of cellular particles (CPs) that interact via short range contact interactions, characterized by an attractive (adhesive interaction) and a repulsive (excluded volume interaction) component. The time evolution of the spatial conformation of the multicellular system is determined by following the trajectories of all CPs through numerical integration of their equations of motion. Here we present CPD simulation results for the fusion of both spherical and cylindrical multi-cellular aggregates. First, we calibrate the relevant CPD model parameters for a given cell type by comparing the CPD simulation results for the fusion of two spherical aggregates to the corresponding experimental results. Next, CPD simulations are used to predict the time evolution of the fusion of cylindrical aggregates. The latter is relevant for the formation of tubular multi-cellular structures (i.e., primitive blood vessels) created by the novel bioprinting technology. Work supported by NSF [PHY-0957914]. Computer time provided by the University of Missouri Bioinformatics Consortium.

  18. Vib--rotational energy distributions and relaxation processes in pulsed HF chemical lasers

    International Nuclear Information System (INIS)

    Ben-Shaul, A.; Kompa, K.L.; Schmailzl, U.

    1976-01-01

    The rate equations governing the temporal evolution of photon densities and level populations in pulsed F+H 2 →HF+H chemical lasers are solved for different initial conditions. The rate equations are solved simultaneously for all relevant vibrational--rotational levels and vibrational--rotational P-branch transitions. Rotational equilibrium is not assumed. Approximate expressions for the detailed state-to-state rate constants corresponding to the various energy transfer processes (V--V, V--R,T, R--R,T) coupling the vib--rotational levels are formulated on the basis of experimental data, approximate theories, and qualitative considerations. The main findings are as follows: At low pressures, R--T transfer cannot compete with the stimulated emission, and the laser output largely reflects the nonequilibrium energy distribution in the pumping reaction. The various transitions reach threshold and decay almost independently and simultaneous lasing on several lines takes place. When a buffer gas is added in excess to the reacting mixture, the enhanced rotational relaxation leads to nearly single-line operation and to the J shift in lasing. Laser efficiency is higher at high inert gas pressures owing to a better extraction of the internal energy from partially inverted populations. V--V exchange enhances lasing from upper vibrational levels but reduces the total pulse intensity. V--R,T processes reduce the efficiency but do not substantially modify the spectral output distribution. The photon yield ranges between 0.4 and 1.4 photons/HF molecule depending on the initial conditions. Comparison with experimental data, when available, is fair

  19. 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.

  20. Synergic nature of dielectric relaxation process in the layered perovskite halide salts: The case of 1,3- diammoniumpropylenetetrabromocadmate compound

    Science.gov (United States)

    Staśkiewicz, Beata

    2018-06-01

    The negative thermal expansion (NTE) property was a prototype to discuss the origin of difference between classical Debye relaxation process and the non-Debye behavior in the layered perovskite halide salt of chemical formula NH3(CH2)3NH3CdBr4. The analysis has been taken by dielectric relaxation spectroscopy measurements in almost six decades in frequency 5 × 102 ≤ f(ω) ≤ 1.2 × 108 and in the temperature range 315 ≤ T(K) ≤ 390. It was shown that the investigated sample exhibit an antiferrodistortive nature of phase transition between two orthorhombic structural modifications i.e. Pnma (phase I) and Ima2 (phase II) at Tc1(I → II) = 326 K, leading from an antiferroelectric to a paraelectric phase. The involvement of an odd number of carbon atoms in the alkylammonium chains in dielectric properties of examined sample is proved. Higher structural modifications, i.e. Ima2 (phase II) and P21/m (phase III), have shown significant deviations from a regular circle on the Cole-Cole diagram. Presented experimental observations are essentially important for the theoretical explanation of relaxation processes in analyzed organic - inorganic compound crystallizing in a perovskite-like topology and may provide new perspective on the fundamental aspect of relaxation response in "diammonium" series.

  1. Electronic relaxation processes in polyatomic molecules. Progress report, October 1, 1975--September 30, 1976

    International Nuclear Information System (INIS)

    Lim, E.C.

    1976-09-01

    Excitation energy dependence of radiationless decay rate under collision-free conditions was utilized as a probe of intramolecular vibrational relaxation in tetracene and pentacene. The results give evidence of vibrational relaxation which competes with electronic relaxation. The substitution dependence of T 1 (nπ*) → S 0 radiationless transition in monocyclic diazines and the temperature dependence of S 1 non-radiative decay rate in alcoholic solutions of polycyclic monoazines indicate that the vibronic interaction between the lowest energy nπ* and ππ* states leads to a rapid radiationless deactivation of the lower of the two electronic states. Finally, a photon-counting spectrofluorometer of very high sensitivity was constructed, and it was used to record T 2 → T 1 fluorescence in bromoanthracenes and S 2 → S 1 fluorescence in azulene. These spectra represent the first bona-fide, or the most convincing, observation of fluorescence between excited electronic states

  2. About relaxation phenomena and transport processing in a fully ionized non-ideal plasma

    International Nuclear Information System (INIS)

    Baimbetov, F.B.; Iztleuov, N.T.

    1999-01-01

    In this report correlation effects for non-ideal plasma are accounted in the so called pseudopotentials. The accounting of high order correlation influences in the pseudopotential lead to the strongly screened potential. Kinetic equation with pseudopotential is cited. The equations which describe the relaxation of the difference of directed velocities of plasma particles, and frequency of particle collision which determines relaxation of temperature for non-ideal plasma are obtained. On basis of mentioned kinetic equation the transport equation is obtained as well

  3. Ultrafast Physics Behind the Nonradiative Relaxation Process of Chromium Ions in Forsterite Crystals.

    Science.gov (United States)

    Demos, Stavros Gregorios

    The nonradiative relaxation following photoexcitation has been studied in Cr^{4+} -doped forsterite (Mg_2SiO _4) using picosecond laser excitation and ultrasensitive photon counting detection. The experimental techniques utilized were time resolved antiStokes Raman scattering and up-converted hot and ordinary luminescence. The up-converted hot luminescence technique allowed the investigation of the upper state nonradiative relaxation of the excited state manifold of Cr^{4+ }-doped forsterite. The excitation involves the absorption of two photons per photoexcited ion in a two-step absorption. Discrete peaks are observed in the hot up-converted luminescence spectrum and are attributed to the population of nonequilibrium vibronic levels during the deexcitation of the ions by phonon emission. This work reveals that the phonon modes participating in the initial steps of the nonradiative relaxation of the photoexcited ions have energies 218 +/- 20, 325 +/- 20, 365 +/- 20 and 513 +/- 12 cm^ {-1}. The shape of the luminescence spectral envelope suggests two electronic bottlenecks at ~2.1 and ~2.45 eV associated with slower rates of vibrational relaxation at different parts of the excited state manifold. Time resolved measurements indicated that the average time for phonon emission is of the order of hundreds of fs. Information on the nonequilibrium phonon dynamics of the 225, 335 and 370 cm^{-1} modes of forsterite has been obtained using time resolved Raman scattering. Laser pulses of 450 fs in duration and 590 nm in wavelength were used to excite the Cr ions 2.1 eV above the ground state. The probe pulses (obtained from the same laser) are monitoring the nonequilibrium phonon population through the intensity of the antiStokes Raman lines at various pump-probe delay times. Experiments were performed at room and liquid nitrogen temperatures. The observed nonequilibrium phonon populations are associated with the overall complex nonradiative decay following the excitation of

  4. Study of conduction mechanisms and relaxation processes in NiCl2-PVA composites

    International Nuclear Information System (INIS)

    Basha, A.F.; Amin, M.; Abdel Samad, H.A.

    1985-07-01

    Electric conduction measurements were made at different temperatures and fields on thin films NiCl 2 -PVA composites prepared by casting. The conduction is assumed to be generally ionic in nature and polarization contribution is suggested to operate mainly at higher temperatures. Space-charge limited conduction and relaxation phenomena have been observed. The obtained results made it possible to determine a complete set of conduction parameters including carrier mobility, carrier concentration, traps density, Fermi energy, activation energy, etc. (author)

  5. 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.

  6. Process of optical excitation and relaxation of color center in synthetic diamond and its application to optoelectronics

    International Nuclear Information System (INIS)

    Nishida, Yoshio

    1989-01-01

    Irradiation of high-pressure synthesized diamond is carried out by using a nuclear reactor or a linac. Then, the effect of annealing on the color centers is observed. A study is made to identify different color centers and to provide techniques to control their introduction. Investigations cover the relation of color center formation with annealing temperature, dependence of color center formation on radiation dose, migration of H3 center and hydrogen, and applicability of five different color centers to optoelectronics. Next, a study is made of the formation and relaxation of the nitrogen vacancy (NV) center in a metastable excited state produced by optical excitation. An optical gain is essential to provide laser. Optical amplification is measured at the vibronic emission band of the NV center. An increase in absorption is detected, indicating that the NV center will not provide laser. In the optical excitation-relaxation process, the relaxation proceeds via a metastable state. Finally, hole burning of ZPL of the NV center is observed in the temperature range from 20K to 80K, and some of its features are described. (N.K.)

  7. Quantum process tomography with informational incomplete data of two J-coupled heterogeneous spins relaxation in a time window much greater than T1

    Science.gov (United States)

    Maciel, Thiago O.; Vianna, Reinaldo O.; Sarthour, Roberto S.; Oliveira, Ivan S.

    2015-11-01

    We reconstruct the time dependent quantum map corresponding to the relaxation process of a two-spin system in liquid-state NMR at room temperature. By means of quantum tomography techniques that handle informational incomplete data, we show how to properly post-process and normalize the measurements data for the simulation of quantum information processing, overcoming the unknown number of molecules prepared in a non-equilibrium magnetization state (Nj) by an initial sequence of radiofrequency pulses. From the reconstructed quantum map, we infer both longitudinal (T1) and transversal (T2) relaxation times, and introduce the J-coupling relaxation times ({T}1J,{T}2J), which are relevant for quantum information processing simulations. We show that the map associated to the relaxation process cannot be assumed approximated unital and trace-preserving for times greater than {T}2J.

  8. Influence of Na doping on the magnetic relaxation processes of magnetite

    International Nuclear Information System (INIS)

    Torres, C.; Arias, A. Gonzalez; Hisatake, K.; Francisco, C. de; Hernandez-Gomez, P.; Kim, C.O.; Kim, D.J.

    2007-01-01

    The relaxation of the initial magnetic permeability was measured in polycrystalline Na-doped magnetite samples, with nominal composition Na x Fe 3- x O 4 (x ranging from 0 to 0.05), by means of the magnetic disaccommodation (DA) technique. We found that the increasing amount of Na ions modifies the DA spectra and a very different behaviour depending on the sintering atmosphere. These results were discussed in terms of the presence of Na ions in the magnetite lattice, giving rise to certain modifications in their neighbourhood

  9. On thermodynamics of relaxation and creep processes in the theory of viscoelastic materials with fading memory

    International Nuclear Information System (INIS)

    Paglietti, A.

    1978-01-01

    This paper is concerned with the thermodynamical theory of materials with fading memory exhibiting the creep and relaxation properties. It is shown that, once the current thermodynamical approach is followed, the second principle of thermodynamics implies for these materials further restrictions on the free-energy functional in addition to the well-known ones deduced in the general theory of materials with fading memory. The possibility of an experimental check of the current approach and the possibility of an alternative and more general approach are briefly discussed. (author)

  10. Influence of E-beam irradiation on dielectric relaxation of recycled polypropylene

    International Nuclear Information System (INIS)

    Fazilova, Z.; Gafurov, U.; Tolstov, A.

    2004-01-01

    Full text: The dielectric relaxation connected with molecular groups and polymer chain mobility for un-irradiated and e-beam irradiated recycled polypropylene was investigated. It was studied films of samples produced from virgin (initial) and e- beam irradiated of the polymer granules (E-beam source with 5 MeV energy). The dielectric losses were measured with temperature increasing and decreasing regime. The losses were measured with E8-4 bridge help (the frequency is 1kH). Heating velocity was 2 grad/min. The dielectric losses did not appeared in minus temperature region for the initial polypropylene samples. The measurement in temperature increasing and decreasing shows that the relaxation peak at ∼ 35 o C for un-irradiated and ∼70 o C for irradiated polymer samples connected with macromolecular segments mobility with water molecular groups participation. The main relaxation peak (higher 100 o C) shifts after e-beam irradiation is result of the cross-links formation. ) The peak connected with macromolecular segments mobility in polymer amorphous regions (β-relaxation process). In irradiated polypropylene on IR spectroscopy data oxygen molecular groups is increased. The molecular groupings form inter-molecular hydrogen bonds. The intermolecular bonds also hindered molecular groups and macromolecular mobility. The e-beam stimulated cross-links formation was confirmed by method of sol-gel analyses. The work was supported by STCU Fund (Project No 3009)

  11. Self-similarly evolving and minimally dissipated stable states of plasmas realized after relaxation and self-organization processes

    International Nuclear Information System (INIS)

    Kondoh, Yoshiomi; Hakoiwa, Toru; Okada, Akihito; Kobayashi, Naohiro; Takahashi, Toshiki

    2006-01-01

    A novel set of simultaneous eigenvalue equations having dissipative terms are derived to find self-similarly evolving and minimally dissipated stable states of plasmas realized after relaxation and self-organization processes. By numerically solving the set of eigenvalue equations in a cylindrical model, typical spatial profiles of plasma parameters, electric and magnetic fields and diffusion factors are presented, all of which determine self-consistently with each other by physical laws and mutual relations among them, just as in experimental plasmas. (author)

  12. Formation and relaxation processes of photoinduced defects in a Ge-doped SiO2 glass

    International Nuclear Information System (INIS)

    Yamaguchi, M.; Saito, K.; Ikushima, A.J.

    2002-01-01

    The defect centers induced by ArF laser irradiation in Ge-doped SiO 2 have been investigated by the electron-spin resonance method. In order to observe formation and relaxation processes of the defects, step annealing has been carried out after the irradiation at 77 K. The thermally induced decay of the self-trapped hole (STH) and formation of the so-called Ge(2) centers have been observed with increasing temperature. The result suggests that the holes are transferred from the STH to the Ge(2)

  13. Study of relaxation processes and uniaxial anisotropy in the Europium Gallium Garnet epitaxial films

    International Nuclear Information System (INIS)

    Mukhopadhyay, P.

    1987-04-01

    We report here the magnetic properties of Europium-Gallium Garnet LPE films of the type Eu x Y 3-x Fe 5-y Ga y O 12 (where O< x<1.2 and 1< y<1.1). The mechanism by which the magnetic moments relax in Eu or Sm Garnets is still not fully understood. We have made studies on Eu-Ga garnet films and explain some of the results observed in these films. Pb and Pt ions are always found as impurities in our films. Pb ions contribute to the anisotropy in the film. Most of the experimental results can be explained with the three sub lattice model. The shape of the FMR line width shows strong sensitivity towards the surface impurities. (author). 18 refs, 6 figs, 1 tab

  14. Modeling and simulation of the deposition/relaxation processes of polycrystalline diatomic structures of metallic nitride films

    Science.gov (United States)

    García, M. F.; Restrepo-Parra, E.; Riaño-Rojas, J. C.

    2015-05-01

    This work develops a model that mimics the growth of diatomic, polycrystalline thin films by artificially splitting the growth into deposition and relaxation processes including two stages: (1) a grain-based stochastic method (grains orientation randomly chosen) is considered and by means of the Kinetic Monte Carlo method employing a non-standard version, known as Constant Time Stepping, the deposition is simulated. The adsorption of adatoms is accepted or rejected depending on the neighborhood conditions; furthermore, the desorption process is not included in the simulation and (2) the Monte Carlo method combined with the metropolis algorithm is used to simulate the diffusion. The model was developed by accounting for parameters that determine the morphology of the film, such as the growth temperature, the interacting atomic species, the binding energy and the material crystal structure. The modeled samples exhibited an FCC structure with grain formation with orientations in the family planes of , and . The grain size and film roughness were analyzed. By construction, the grain size decreased, and the roughness increased, as the growth temperature increased. Although, during the growth process of real materials, the deposition and relaxation occurs simultaneously, this method may perhaps be valid to build realistic polycrystalline samples.

  15. Relaxation dynamics of the conductive processes for PbNb2O6 ferroelectric ceramics in the frequency and time domain

    International Nuclear Information System (INIS)

    Gonzalez, R L; Leyet, Y; Guerrero, F; Guerra, J de Los S; Venet, M; Eiras, J A

    2007-01-01

    The relaxation dynamics of the conductive process present in PbNb 2 O 6 piezoelectric ceramics was investigated. A relaxation function in the time domain, Φ(t), was found from the frequency dependence of the dielectric modulus (imaginary component, M'') by using a relaxation function in the frequency domain, F*(ω). The best relaxation function, F*(ω), was found to be a Cole-Cole distribution function, in which relaxation characteristic parameters, such as α and τ CC , are involved. On the other hand, the relaxation function, Φ(t), obtained by the time domain method, was found to be a Kohlrausch-Williams-Watts (KWW) function type. The thermal evolution of the characteristics parameters of the KWW function (β and τ*) was analysed. The values of the activation energy (E a ), obtained in the whole investigated temperature interval, suggest the existence of a relaxation mechanism (a conductive process), which may be interpreted by an ion hopping between neighbouring sites within the crystalline lattice. The results are corroborated with the formalism of the AC conductivity

  16. 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

  17. Dielectric and mechanical relaxation in isooctylcyanobiphenyl (8*OCB)

    Energy Technology Data Exchange (ETDEWEB)

    Pawlus, S; Mierzwa, M; Paluch, M; Rzoska, S J [Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice (Poland); Roland, C M, E-mail: michal.mierzwa@us.edu.p [Chemistry Division, Naval Research Laboratory, Code 6120, Washington, DC 20375-5342 (United States)

    2010-06-16

    The dynamics of isooctylcyanobiphenyl (8*OCB) was characterized using dielectric and mechanical spectroscopies. This isomer of the liquid crystalline octylcyanobiphenyl (8OCB) vitrifies during cooling or on application of pressure, exhibiting the typical features of glass-forming liquids: non-Debye relaxation function, non-Arrhenius temperature dependence of the relaxation times, {tau}{sub {alpha}}, a dynamic crossover at T {approx} 1.6T{sub g}. This crossover is evidenced by changes in the behavior of both the peak shape and the temperature dependence of {tau}{sub {alpha}}. The primary relaxation time at the crossover, 2 ns at ambient pressure, is the smallest value reported to date for any molecular liquid or polymer. Interestingly, at all temperatures below this crossover, {tau}{sub {alpha}}and the dc conductivity remain coupled (i.e., conform to the Debye-Stokes-Einstein relation). Two secondary relaxations are observed in the glassy state, one of which is identified as the Johari-Goldstein process. Unlike the case for 8OCB, no liquid crystalline phase could be attained for 8*OCB, demonstrating that relatively small differences in chemical structure can effect substantial changes in the intermolecular potential.

  18. Guinea-pig interpubic joint (symphysis pubica relaxation at parturition: Underlying cellular processes that resemble an inflammatory response

    Directory of Open Access Journals (Sweden)

    Muñoz-de-Toro Mónica

    2003-11-01

    Full Text Available Abstract Background At term, cervical ripening in coordination with uterine contractions becomes a prerequisite for a normal vaginal delivery. Currently, cervical ripening is considered to occur independently from uterine contractions. Many evidences suggest that cervical ripening resembles an inflammatory process. Comparatively little attention has been paid to the increased flexibility of the pelvic symphysis that occurs in many species to enable safe delivery. The aim of this study was to investigate whether the guinea-pig interpubic joint relaxation process observed during late pregnancy and parturition resembles an inflammatory process. Methods Samples of pubic symphysis were taken from pregnant guinea-pigs sacrificed along gestation, parturition and postpartum. Serial sections of paraffin-embedded tissues were used to measure the interpubic distance on digitalized images, stained with Giemsa to quantify leukocyte infiltration and to describe the vascular area changes, or studied by the picrosirius-polarization method to evaluate collagen remodeling. P4 and E2 serum levels were measured by a sequential immunometric assay. Results Data showed that the pubic relaxation is associated with an increase in collagen remodeling. In addition, a positive correlation between E2 serum levels and the increase in the interpubic distance was found. On the other hand, a leukocyte infiltration in the interpubic tissue around parturition was described, with the presence of almost all inflammatory cells types. At the same time, histological images show an increase in vascular area (angiogenesis. Eosinophils reached their highest level immediately before parturition; whereas for the neutrophilic and mononuclear infiltration higher values were recorded one day after parturition. Correlation analysis showed that eosinophils and mononuclear cells were positively correlated with E2 levels, but only eosinophilic infiltration was associated with collagen remodeling

  19. The influence of secondary processing on the structural relaxation dynamics of fluticasone propionate.

    Science.gov (United States)

    Depasquale, Roberto; Lee, Sau L; Saluja, Bhawana; Shur, Jagdeep; Price, Robert

    2015-06-01

    This study investigated the structural relaxation of micronized fluticasone propionate (FP) under different lagering conditions and its influence on aerodynamic particle size distribution (APSD) of binary and tertiary carrier-based dry powder inhaler (DPI) formulations. Micronized FP was lagered under low humidity (LH 25 C, 33% RH [relative humidity]), high humidity (HH 25°C, 75% RH) for 30, 60, and 90 days, respectively, and high temperature (HT 60°C, 44% RH) for 14 days. Physicochemical, surface interfacial properties via cohesive-adhesive balance (CAB) measurements and amorphous disorder levels of the FP samples were characterized. Particle size, surface area, and rugosity suggested minimal morphological changes of the lagered FP samples, with the exception of the 90-day HH (HH90) sample. HH90 FP samples appeared to undergo surface reconstruction with a reduction in surface rugosity. LH and HH lagering reduced the levels of amorphous content over 90-day exposure, which influenced the CAB measurements with lactose monohydrate and salmeterol xinafoate (SX). CAB analysis suggested that LH and HH lagering led to different interfacial interactions with lactose monohydrate but an increasing adhesive affinity with SX. HT lagering led to no detectable levels of the amorphous disorder, resulting in an increase in the adhesive interaction with lactose monohydrate. APSD analysis suggested that the fine particle mass of FP and SX was affected by the lagering of the FP. In conclusion, environmental conditions during the lagering of FP may have a profound effect on physicochemical and interfacial properties as well as product performance of binary and tertiary carrier-based DPI formulations.

  20. 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.

  1. Experimental evidence for simultaneous relaxation processes in super spin glass γ-Fe{sub 2}O{sub 3} nanoparticle system

    Energy Technology Data Exchange (ETDEWEB)

    Nikolic, V.; Perovic, M., E-mail: mara.perovic@vinca.rs; Kusigerski, V.; Boskovic, M.; Mrakovic, A.; Blanusa, J.; Spasojevic, V. [University of Belgrade, Condensed Matter Physics Laboratory, Institute of Nuclear Sciences Vinca (Serbia)

    2015-03-15

    Spherical γ-Fe{sub 2}O{sub 3} nanoparticles with the narrow size distribution of (5 ± 1) nm were synthesized by the method of thermal decomposition from iron acetyl acetonate precursor. The existence of super spin-glass state at low temperatures and in low applied magnetic fields was confirmed by DC magnetization measurements on a SQUID magnetometer. The comprehensive investigation of magnetic relaxation dynamics in low-temperature region was conducted through the measurements of single-stop and multiple stop ZFC memory effects, ZFC magnetization relaxation, and AC susceptibility measurements. The experimental findings revealed the peculiar change of magnetic relaxation dynamics at T ≈ 10 K, which arose as a consequence of simultaneous existence of different relaxation processes in Fe{sub 2}O{sub 3} nanoparticle system. Complementarity of the applied measurements was utilized in order to single out distinct relaxation processes as well as to elucidate complex relaxation mechanisms in the investigated interacting nanoparticle system.

  2. Influence of Nanodisperse Metal Fillers on the Viscoelastic Properties and Processes of Mechanical Relaxation of Polymer Systems

    Science.gov (United States)

    Kolupav, B. B.; Kolupaev, B. S.; Levchuk, V. V.; Maksimtsev, Yu. R.; Sidletskii, V. A.

    2017-05-01

    The results of research into the viscoelastic properties and processes of mechanical relaxation of polyvinylchloride (PVC) containing Cu nanoparticles obtained by means of electroerosion crushing and electrohydraulic destruction of agglomerates of disperse Cu in the presence of an ultrasonic field are presented. It is shown that, in the case of longitudinal shear deformation at a frequency of 0.4 × 106 s-1 over a wide range of temperatures and content of ingredients, viscoelastic phenomena depending on structural changes in the PVC system occur. An analysis of quantitative results of the elastic and viscoelastic deformation of a body is carried out taking into account the energy and entropy components of interaction of the polymer and filler at their interface.

  3. 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

  4. Effect of radiation and non-Maxwellian electron distribution on relaxation processes in an atmospheric cesium seeded argon plasma

    International Nuclear Information System (INIS)

    Borghi, C.A.; Veefkind, A.; Wetzer, J.M.

    1982-03-01

    A model, describing the time dependent behaviour of a noble gas MHD generator plasma, has been set up. With this model it is possible to calculate the relaxation for ionization or recombination as a response to a stepwise temperature development, once the initial and final conditions are given. In model radiative transitions and a deviation from Maxwellian electron distribution are included. Radiation causes an enhancement of both the ionization relaxation time and the recombination relaxation time. A non-Maxwellian electron distribution results in an increase of the relaxation time for an ionizing plasma because of an underpopulation of the high energy electrons. A decrease of the relaxation time for a recombining plasma is caused by an overpopulation of high energy electrons. The relaxation time is strongly dependent on the seed ratio and the temperature step. (Auth.)

  5. Elevated intrabolus pressure identifies obstructive processes when integrated relaxation pressure is normal on esophageal high-resolution manometry.

    Science.gov (United States)

    Quader, Farhan; Reddy, Chanakyaram; Patel, Amit; Gyawali, C Prakash

    2017-07-01

    Elevated integrated relaxation pressure (IRP) on esophageal high-resolution manometry (HRM) identifies obstructive processes at the esophagogastric junction (EGJ). Our aim was to determine whether intrabolus pressure (IBP) can identify structural EGJ processes when IRP is normal. In this observational cohort study, adult patients with dysphagia and undergoing HRM were evaluated for endoscopic evidence of structural EGJ processes (strictures, rings, hiatus hernia) in the setting of normal IRP. HRM metrics [IRP, distal contractile integral (DCI), distal latency (DL), IBP, and EGJ contractile integral (EGJ-CI)] were compared among 74 patients with structural EGJ findings (62.8 ± 1.6 yr, 67.6% women), 27 patients with normal EGD (52.9 ± 3.2 yr, 70.3% women), and 21 healthy controls (27.6 ± 0.6 yr, 52.4% women). Findings were validated in 85 consecutive symptomatic patients to address clinical utility. In the primary cohort, mean IBP (18.4 ± 0.9 mmHg) was higher with structural EGJ findings compared with dysphagia with normal EGD (13.5 ± 1.1 mmHg, P = 0.002) and healthy controls (10.9 ± 0.9 mmHg, P 0.05 for each comparison). During multiple rapid swallows, IBP remained higher in the structural findings group compared with controls ( P = 0.02). Similar analysis of the prospective validation cohort confirmed IBP elevation in structural EGJ processes, but correlation with dysphagia could not be demonstrated. We conclude that elevated IBP predicts the presence of structural EGJ processes even when IRP is normal, but correlation with dysphagia is suboptimal. NEW & NOTEWORTHY Integrated relaxation pressure (IRP) above the upper limit of normal defines esophageal outflow obstruction using high-resolution manometry. In patients with normal IRP, elevated intrabolus pressure (IBP) can be a surrogate marker for a structural restrictive or obstructive process at the esophagogastric junction (EGJ). This has the potential to augment the clinical value of

  6. The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation.

    Science.gov (United States)

    de Oliveira, Luciana Renata; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C

    2014-08-14

    We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their

  7. The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation

    International Nuclear Information System (INIS)

    Oliveira, Luciana Renata de; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C.

    2014-01-01

    We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their “far from equilibrium behavior,” hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative “external vector field” whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the “plasticity property” of biological

  8. Process of advective diffusive enrichment using differential gradients and the effects of variations in relaxation times

    International Nuclear Information System (INIS)

    Suarez Antola R.; Bernasconi, G.; Bertolotti, Angel

    1995-01-01

    A multicomponent solution is considered in advective diffusion chambers between two half-permeable barriers. A mathematical model is developed to calculate the concentration fields in the chamber. A new enrichment process is proposed and assessed using a digital simulation of space-time dynamics, based on the analytical solution of the model

  9. Relaxation and excitation electronic processes in dielectrics irradiated by ultrafast IR and VUV pulses; Processus electroniques d'excitation et de relaxation dans les solides dielectriques excites par des impulsions IR et XUV ultracourtes

    Energy Technology Data Exchange (ETDEWEB)

    Gaudin, J

    2005-11-15

    We studied excitation and relaxation of electrons involved during interaction of visible and VUV femtosecond pulses with dielectrics. The generated population of hot electrons, having energy of few eV to few tens of eV above the bottom of the conduction band, is responsible of phenomena ranging to defect creation to optical breakdown. Owing to two techniques: photoemission and transient photoconductivity we improve the understanding of the The first photoemission experiments deal with dielectrics irradiated by 30 fs IR pulses. The photoemission spectra measured show a large population of electrons which energy rise up to 40 eV. We interpret this result in terms of a new absorption process: direct multi-photons inter-branch transitions. The 2. type of photoemission experiments are time resolved 'pump/probe' investigation. We study the relaxation of electrons excited by a VUV pulses. We used the high order harmonics (HOH) as light sources. We found surprisingly long decay time in the range of ps timescale. Last type of experiments is photoconductivity studies of diamond samples. Using HOH as light source we measure the displacement current induced by excited electrons in the conduction band. Those electrons relax mainly by impact ionisation creating secondary electrons. Hence by probing the number of electrons we were able to measure the efficiency of these relaxation processes. We observe a diminution of this efficiency when the energy of exciting photons is above 20 eV. Owing to Monte-Carlo simulation we interpret this result in terms of band structure effect. (author)

  10. Uncovering molecular relaxation processes with nonlinear spectroscopies in the deep UV

    International Nuclear Information System (INIS)

    West, Brantley A.; Molesky, Brian P.; Giokas, Paul G.; Moran, Andrew M.

    2013-01-01

    Highlights: • We discuss the outlook for multidimensional spectroscopies in the deep UV. • Photophysics are examined in small DNA components at cryogenic temperatures. • Wavepacket motions are detected in ring-opening systems with 2DUV spectroscopy. • Measurements of electronic wavepacket motions in molecules are proposed. - Abstract: Nonlinear laser spectroscopies in the deep UV spectral range are motivated by studies of biological systems and elementary processes in small molecules. This perspective article discusses recent technical advances in this area with a particular emphasis on diffractive optic based approaches to four-wave mixing spectroscopies. Applications to two classes of systems illustrate present experimental capabilities. First, experiments on DNA components at cryogenic temperatures are used to uncover features of excited state potential energy surfaces and vibrational cooling mechanisms. Second, sub-200 fs internal conversion processes and coherent wavepacket motions are investigated in cyclohexadiene and α-terpinene. Finally, we propose new experimental directions that combine methods for producing few-cycle UV laser pulses in noble gases with incoherent detection methods (e.g., photoionization) in experiments with time resolution near a singlefemtosecond. These measurements are motivated by knowledge of extremely fast non-adiabatic dynamics and the resolution of electronic wavepacket motions in molecules

  11. 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...

  12. Influence of relaxation processes in polymers on energy transfer by triplet levels

    International Nuclear Information System (INIS)

    Ibraev, N.Kh.; Zhunusbekov, A.M.

    1996-01-01

    Temperature influence on triplet-triplet (T-T) energy transfer between molecules of eosin and 3,4-benzopyrene is studied. Polyvenylbuteryl films have been used in capacity of polymer matrix. Calculation has being carried out on spectral-kinetic unit. It is revealed, that 3,4-benzopyrene triplets have been formed in polymer matrix after end of T-T energy transfer. These triplets join in a reaction of mixed triplet-triplet annihilation with non-blow out triplets of eosin and its sensitize slowed fluorescence (SF) of donor. This explains non-exponent character of eosin's dumping kinetics. Non-linear dependence of SF output ration to eosin phosphorescence output under presence of 3,4-benzopyrene molecules in film indicates on process of mixed annihilation. Fractal character of SF donor and acceptor has been evidenced about microscopical distribution of phosphor in polymer. 13 refs., 5 figs

  13. Effects of electric paravertebral muscle relaxation processes in the athletes heart

    Directory of Open Access Journals (Sweden)

    D. V. Syshko

    2013-02-01

    Full Text Available Influence of paravertebrals miorelaxation on electric processes in a heart at sportsmen is studied. Paravertebrals miorelaxation was the complex of exercises in a water environment directed on the decline of tone of paravertebral muscles. Before and after it was used of paravertebrals miorelaxation registered the indexes of electrocardiography at the sportsmen engaged in the Greek-Roman fight (n=22 by football (n=24 and heavy athletics (n=25. It is got, that at the sportsmen of engaged in the Greek -Roman fight after paravertebrals miorelaxation QRS and QT were it was increased, and R-R and PQ went down. At the sportsmen of engaged in heavy athletics HR and PQ went down after paravertebrals miorelaxation, R-R, QRS and QT were it was increased. At the sportsmen of getting busy by football the PQ interval shortened, and QRS and QT has multiplied. Findings testify to the presence of different mechanisms of adaptation of the conducting system of heart in the conditions of influencing of paravertebrals miorelaxation. These distinctions are fated by two basic factors: by the functional being of the cardio-vessels system on the whole and functional being of sine knot and conducting system of heart in particular.

  14. In vivo measurements of the T1 relaxation processes in the bone marrow in patients with myelodysplastic syndrome

    International Nuclear Information System (INIS)

    Jensen, K.E.; Nielsen, H.; Thomsen, C.; Soerensen, P.G.; Karle, H.; Christoffersen, P.; Henriksen, O.; Hvidovre Hospital, Copenhagen; Hvidovre Hospital, Copenhagen

    1989-01-01

    Nine patients with myelodysplastic syndrome (MDS) were examined with magnetic resonance imaging and in vivo T1 relaxation time measurements of the vertebral bone marrow in a 1.5 tesla whole body scanner. Two patients underwent transformation to acute myeloid leukemia and were evaluated at follow-up examinations. At the time of diagnosis the T1 relaxation times of the vertebral bone marrow were significantly prolonged compared with normal values. The T1 relaxation times of the vertebral bone marrow in patients with MDS showed significantly lower values compared with patients with acute leukemia and did not differ from patients with polycythemia vera. (orig.)

  15. Statistical mechanical approach to secondary processes and structural relaxation in glasses and glass formers: a leading model to describe the onset of Johari-Goldstein processes and their relationship with fully cooperative processes.

    Science.gov (United States)

    Crisanti, A; Leuzzi, L; Paoluzzi, M

    2011-09-01

    The interrelation of dynamic processes active on separated time-scales in glasses and viscous liquids is investigated using a model displaying two time-scale bifurcations both between fast and secondary relaxation and between secondary and structural relaxation. The study of the dynamics allows for predictions on the system relaxation above the temperature of dynamic arrest in the mean-field approximation, that are compared with the outcomes of the equations of motion directly derived within the Mode Coupling Theory (MCT) for under-cooled viscous liquids. By varying the external thermodynamic parameters, a wide range of phenomenology can be represented, from a very clear separation of structural and secondary peak in the susceptibility loss to excess wing structures.

  16. 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.

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

    Science.gov (United States)

    Mauck, Catherine McKay

    The development of organic photovoltaic devices benefits from understanding the fundamental processes underlying charge generation in thin films of organic semiconductors. This dissertation exploits model systems of pi-stacked chromophores such as perylene-3,4:9,10-bis(dicarboximide) (PDI) and 3,6-bis(aryl)diketopyrrolopyrrole (DPP) to study these processes using ultrafast electronic and vibrational spectroscopy. In particular, the characterization of covalent molecular dimers, thin films, and solution aggregates can reveal how supramolecular order affects photophysical properties. PDI and DPP are organic semiconductors that have been widely studied in organic photovoltaics, due to their strong visible absorption and excellent chemical stability. As solution-phase monomers, they are highly fluorescent, but in the thin film environment of photovoltaic devices these planar aromatic molecules couple to one another, stacking largely through pi-pi interactions. In self-assembled stacks of PDI, strong interchromophore coupling may disrupt charge separation through the formation of excimer states, preventing the generation of free carriers. By studying molecular dimers of PDI with different pi-stacked geometry, femtosecond visible pump mid-infrared probe spectroscopy allows direct observation of the structural dynamics associated with excimer state relaxation, showing that this low-energy state is primarily coupled to the core modes that shift as planarization and rotation lead to the most stable excimer geometry. PDI is also able to undergo singlet fission in thin films and aggregates. Singlet fission is the process in which a singlet excited state is downconverted into two triplet excitons, when the energy of its first singlet excited state is at least twice the energy of the lowest triplet state in an appropriately coupled molecular system. This spin-allowed, ultrafast process enables a theoretical yield of two charge carriers per incident photon, making it a

  18. Changes in T1 relaxation processes in the bone marrow following treatment in children with acute lymphoblastic leukemia

    International Nuclear Information System (INIS)

    Jensen, K.E.; Thomsen, C.; Henriksen, O.; Hertz, H.; Johansen, H.K.; Yssing, M.

    1990-01-01

    Magnetic resonance imaging (MRI) and T 1 relaxation time measurements of the vertebral bone marrow were performed in 11 children with acute lymphoblastic leukemia (ALL) at diagnosis. Nine of the children were re-examined after chemotherapeutic treatment. The results were compared with histological data from bone marrow biopsies obtained in close association to the MR examinations. Ten age matched children were examined as a control group. A 1.5 Tesla whole body scanner was used for the measurements. The pretreatment T 1 relaxation times of the bone marrow were significantly prolonged, compared to the age matched controls. After chemotherapy the T 1 relaxation times of the children with ALL decreased significantly towards or into the normal range. A significant correlation was found between the T 1 relaxation time and the content of malignant blast cells in the bone marrow. (orig.)

  19. Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Junji, E-mail: j-itou@mail.nissan.co.jp [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Hanaki, Yasunari [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Shen, Qing [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Toyoda, Taro [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer We determined the decay time of photoexcited electrons of Pt/Al{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Faster decay of excited electrons in Pt/Al{sub 2}O{sub 3} leads to its faster oxidation rate. Black-Right-Pointing-Pointer Decreasing excited electron lifetime in Pt/Al{sub 2}O{sub 3} may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al{sub 2}O{sub 3}) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO{sub 2} with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt{sup +} becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt{sup +} returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

  20. Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

    International Nuclear Information System (INIS)

    Ito, Junji; Hanaki, Yasunari; Shen, Qing; Toyoda, Taro

    2012-01-01

    Highlights: ► We determined the decay time of photoexcited electrons of Pt/Al 2 O 3 . ► Faster decay of excited electrons in Pt/Al 2 O 3 leads to its faster oxidation rate. ► Decreasing excited electron lifetime in Pt/Al 2 O 3 may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al 2 O 3 ) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al 2 O 3 and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al 2 O 3 and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO 2 with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt + becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt + returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

  1. Electron spin relaxation governed by Raman processes both for Cu2+ ions and carbonate radicals in KHCO3 crystals: EPR and electron spin echo studies

    Science.gov (United States)

    Hoffmann, Stanislaw K.; Goslar, Janina; Lijewski, Stefan

    2012-08-01

    EPR studies of Cu2+ and two free radicals formed by γ-radiation were performed for KHCO3 single crystal at room temperature. From the rotational EPR results we concluded that Cu2+ is chelated by two carbonate molecules in a square planar configuration with spin-Hamiltonian parameters g|| = 2.2349 and A|| = 18.2 mT. Free radicals were identified as neutral HOCOrad with unpaired electron localized on the carbon atom and a radical anion CO3·- with unpaired electron localized on two oxygen atoms. The hyperfine splitting of the EPR lines by an interaction with a single hydrogen atom of HOCOrad was observed with isotropic coupling constants ao = 0.31 mT. Two differently oriented radical sites were identified in the crystal unit cell. Electron spin-lattice relaxation measured by electron spin echo methods shows that both Cu2+ and free radicals relax via two-phonon Raman processes with almost the same relaxation rate. The temperature dependence of the relaxation rate 1/T1 is well described with the effective Debye temperature ΘD = 175 K obtained from a fit to the Debye-type phonon spectrum. We calculated a more realistic Debye temperature value from available elastic constant values of the crystal as ΘD = 246 K. This ΘD-value and the Debye phonon spectrum approximation give a much worse fit to the experimental results. Possible contributions from a local mode or an optical mode are considered and it is suggested that the real phonon spectrum should be used for the relaxation data interpretation. It is unusual that free radicals in KHCO3 relax similarly to the well localized Cu2+ ions, which suggests a small destruction of the host crystal lattice by the ionizing irradiation allowing well coupling between radical and lattice dynamics.

  2. 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.

  3. Corroborative evidences of TV γ -scaling of the α-relaxation originating from the primitive relaxation/JG β relaxation

    Science.gov (United States)

    Ngai, K. L.; Paluch, M.

    2017-12-01

    Successful thermodynamic scaling of the structural alpha-relaxation time or transport coefficients of glass-forming liquids determined at various temperatures T and pressures P means the data conform to a single function of the product variable TVgamma, where V is the specific volume and gamma is a material specific constant. In the past two decades we have witnessed successful TVgamma-scaling in many molecular, polymeric, and even metallic glass-formers, and gamma is related to the slope of the repulsive part of the intermolecular potential. The advances made indicate TVgamma-scaling is an important aspect of the dynamic and thermodynamic properties of glass-formers. In this paper we show the origin of TVgamma-scaling is not from the structural alpha-relaxation time. Instead it comes from its precursor, the Johari-Goldstein beta-relaxation or the primitive relaxation of the Coupling Model and their relaxation times or tau_0 respectively. It is remarkable that all relaxation times are functions of TVgamma with the same gama, as well as the fractional exponent of the Kohlrausch correlation function of the structural alpha-relaxation. We arrive at this conclusion convincingly based on corroborative evidences from a number of experiments and molecular dynamics simulations performed on a wide variety of glass-formers and in conjunction with consistency with the predictions of the Coupling Model.

  4. 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...

  5. Ionization yield and absorption spectra reveal superexcited Rydberg state relaxation processes in H{sub 2}O and D{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Fillion, J-H [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Dulieu, F [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Baouche, S [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Lemaire, J-L [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Jochims, H W [Institut fuer Physikalische und Theoretische Chemie der Freien Universitaet Berlin, Takustrasse 3, D-14195 Berlin 33 (Germany); Leach, S [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France)

    2003-07-14

    The absorption cross section and the ionization quantum yield of H{sub 2}O have been measured using a synchrotron radiation source between 9 and 22 eV. Comparison between the two curves highlights competition between relaxation processes for Rydberg states converging to the first A-tilde {sup 2}A{sub 1} and to the second B-tilde {sup 2}B{sub 2} excited states of H{sub 2}O{sup +}. Comparison with D{sub 2}O absorption and ionization yields, derived from Katayama et al (1973 J. Chem. Phys. 59 4309), reveals specific energy-dependent deuteration effects on competitive predissociation and autoionization relaxation channels. Direct ionization was found to be only slightly affected by deuteration.

  6. Actuality the process of relaxation on the lessons of physical training on the current stage of higher education

    Directory of Open Access Journals (Sweden)

    Vankova A.U.

    2010-04-01

    Full Text Available Facilities are considered of making healthy for the improvement of ability to resist stress situations of students. Engaged in a physical culture in the net of educational clock must be conducted in the institute of higher before and after the special disciplines. Application of method of relaxation together with musical accompaniment promote claim of higher type of pedagogical organization of employments. A chronic mental overstrain without the sufficient physical discharging results in a nervous overstrain, negative emotions, deficit of time, violation of the mode of labour and rest, reduction of possibility of physical activity.

  7. Extended Thermodynamics of Rarefied Polyatomic Gases: 15-Field Theory Incorporating Relaxation Processes of Molecular Rotation and Vibration

    Directory of Open Access Journals (Sweden)

    Takashi Arima

    2018-04-01

    Full Text Available After summarizing the present status of Rational Extended Thermodynamics (RET of gases, which is an endeavor to generalize the Navier–Stokes and Fourier (NSF theory of viscous heat-conducting fluids, we develop the molecular RET theory of rarefied polyatomic gases with 15 independent fields. The theory is justified, at mesoscopic level, by a generalized Boltzmann equation in which the distribution function depends on two internal variables that take into account the energy exchange among the different molecular modes of a gas, that is, translational, rotational, and vibrational modes. By adopting the generalized Bhatnagar, Gross and Krook (BGK-type collision term, we derive explicitly the closed system of field equations with the use of the Maximum Entropy Principle (MEP. The NSF theory is derived from the RET theory as a limiting case of small relaxation times via the Maxwellian iteration. The relaxation times introduced in the theory are shown to be related to the shear and bulk viscosities and heat conductivity.

  8. Divided-evolution-based pulse scheme for quantifying exchange processes in proteins: powerful complement to relaxation dispersion experiments.

    Science.gov (United States)

    Bouvignies, Guillaume; Hansen, D Flemming; Vallurupalli, Pramodh; Kay, Lewis E

    2011-02-16

    A method for quantifying millisecond time scale exchange in proteins is presented based on scaling the rate of chemical exchange using a 2D (15)N, (1)H(N) experiment in which (15)N dwell times are separated by short spin-echo pulse trains. Unlike the popular Carr-Purcell-Meiboom-Gill (CPMG) experiment where the effects of a radio frequency field on measured transverse relaxation rates are quantified, the new approach measures peak positions in spectra that shift as the effective exchange time regime is varied. The utility of the method is established through an analysis of data recorded on an exchanging protein-ligand system for which the exchange parameters have been accurately determined using alternative approaches. Computations establish that a combined analysis of CPMG and peak shift profiles extends the time scale that can be studied to include exchanging systems with highly skewed populations and exchange rates as slow as 20 s(-1).

  9. Study of relaxation processes in 'metal-ligand' complexes after electron capture decay using the 111In isotope as an example

    International Nuclear Information System (INIS)

    Shpinkova, L.G.; Golubeva, A.S.; Ryasny, O.K.; Nikitin, S.M.; Sorokin, A.A.; Uzbyakova, A.S.

    2003-01-01

    Full text: Complexes of metals with organic ligands are widely used in different scientific and industrial applications, such as analytical chemistry, oil production and refinery, power engineering, water treatment, agriculture, etc. Several hundred complexes are commercially available and there are still intensive works on synthesizing new complexones in order to obtain complexes with required properties. In this connection, it is important to investigate the molecular characteristics of complexes and their structures and correlate with their properties. One of the methods, which proved to provide useful information about metal-ligand complexes behaviour, is the method of time differential perturbed angular γγ-correlation (Tdpa). Numerous works have been devoted to studies of different complexes by this technique. In the Inst. of Nuclear Physics, Lomonosov Moscow State Univ., Moscow, this method was applied to studies of electron capture (EC) after-effects and their influence on the indium-ligand complexes in aqueous solutions. The present work is devoted to studies of relaxation processes in daughter 111 Cd-ligand complexes formed after 111 In EC decay. EC leaves a hole in an inner electronic shell of the daughter atom, which is followed by Auger-process. This process leads to a highly excited state of a daughter atom, which either causes disintegration of a complex into small fragments or relaxation to a stable complex with the daughter atom. TDPAC measurements were performed for a number of 111 In-complexes with acetic and phosphonic ligands. All measurements were performed for neutral aqueous solutions of complexes at room temperature. Three types of molecules containing radioactive daughter 11C d atoms were observed after 111 In decay for all studied complexes. One fraction corresponds to the intact complexes, the second one - to fully disintegrated complexes. The third fraction was characterized by a fast relaxation parameter indicating high transient

  10. 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.

  11. Steepest-entropy-ascent quantum thermodynamic modeling of the relaxation process of isolated chemically reactive systems using density of states and the concept of hypoequilibrium state

    Science.gov (United States)

    Li, Guanchen; von Spakovsky, Michael R.

    2016-01-01

    This paper presents a study of the nonequilibrium relaxation process of chemically reactive systems using steepest-entropy-ascent quantum thermodynamics (SEAQT). The trajectory of the chemical reaction, i.e., the accessible intermediate states, is predicted and discussed. The prediction is made using a thermodynamic-ensemble approach, which does not require detailed information about the particle mechanics involved (e.g., the collision of particles). Instead, modeling the kinetics and dynamics of the relaxation process is based on the principle of steepest-entropy ascent (SEA) or maximum-entropy production, which suggests a constrained gradient dynamics in state space. The SEAQT framework is based on general definitions for energy and entropy and at least theoretically enables the prediction of the nonequilibrium relaxation of system state at all temporal and spatial scales. However, to make this not just theoretically but computationally possible, the concept of density of states is introduced to simplify the application of the relaxation model, which in effect extends the application of the SEAQT framework even to infinite energy eigenlevel systems. The energy eigenstructure of the reactive system considered here consists of an extremely large number of such levels (on the order of 10130) and yields to the quasicontinuous assumption. The principle of SEA results in a unique trajectory of system thermodynamic state evolution in Hilbert space in the nonequilibrium realm, even far from equilibrium. To describe this trajectory, the concepts of subsystem hypoequilibrium state and temperature are introduced and used to characterize each system-level, nonequilibrium state. This definition of temperature is fundamental rather than phenomenological and is a generalization of the temperature defined at stable equilibrium. In addition, to deal with the large number of energy eigenlevels, the equation of motion is formulated on the basis of the density of states and a set of

  12. Characterization of the Ionic Liquid/Electrode Interfacial Relaxation Processes Under Potential Polarization for Ionic Liquid Amperometric Gas Sensor Method Development.

    Science.gov (United States)

    Lin, Lu; Zhao, Peng; Mason, Andrew J; Zeng, Xiangqun

    2018-06-04

    Electrochemical amperometric sensors require a constant or varying potential at the working electrode that drives redox reactions of the analyte for detection. The interfacial redox reaction(s) can result in the formation of new chemical products that could change the initial condition of the electrode/electrolyte interface. If the products are not inert and/or cannot be removed from the system such that the initial condition of the electrode/electrolyte interface cannot be restored, the sensor signal baseline would consequently drift, which is problematic for the continuous and real-time sensors. By setting the electrode potential with the periodical ON-OFF mode, electrolysis can be forestalled during the off mode which can minimize the sensor signal baseline drift and reduce the power consumption of the sensor. However, it is known that the relaxation of the structure in the electrical double layer at the ionic liquid/electrode interface to the steps of the electrode potential is slow. This work characterized the electrode/electrolyte interfacial relaxation process of an ionic liquid based electrochemical gas (IL-EG) sensor by performing multiple potential step experiments in which the potential is stepped from an open circuit potential (OCP) to the amperometric sensing potential at various frequencies with different time periods. Our results showed that by shortening the sensing period as well as extending the idle period (i.e., enlarge the ratio of idle period versus sensing period) of the potential step experiments, the electrode/electrolyte interface is prone to relax to its original state, and thus reduces the baseline drift. Additionally, the high viscosity of the ionic liquids is beneficial for electrochemical regeneration via the implementation of a conditioning step at zero volts at the electrode/electrolyte. By setting the working electrode at zero volts instead of OCP, our results showed that it could further minimize the baseline drift, enhance the

  13. Low frequency dielectric relaxation processes and ionic conductivity of montmorillonite clay nanoparticles colloidal suspension in poly(vinyl pyrrolidone−ethylene glycol blends

    Directory of Open Access Journals (Sweden)

    2008-11-01

    Full Text Available The dielectric dispersion behaviour of montmorillonite (MMT clay nanoparticles colloidal suspension in poly(vinyl pyrrolidone-ethylene glycol (PVP-EG blends were investigated over the frequency range 20 Hz to 1 MHz at 30°C. The 0, 1, 2, 3, 5 and 10 wt% MMT clay concentration of the weight of total solute (MMT+PVP were prepared in PVP-EG blends using EG as solvent. The complex relative dielectric function, alternating current (ac electrical conductivity, electric modulus and impedance spectra of these materials show the relaxation processes corresponding to the micro-Brownian motion of PVP chain, ion conduction and electrode polarization phenomena. The real part of ac conductivity spectra of these materials obeys Jonscher power law σ′(ω =σdc + Aωn in upper frequency end of the measurement, whereas dispersion in lower frequency end confirms the presence of electrode polarization effect. It was observed that the increase of clay concentration in the PVP-EG blends significantly increases the ac conductivity values, and simultaneously reduces the ionic conductivity relaxation time and electric double layer relaxation time, which suggests that PVP segmental dynamics and ionic motion are strongly coupled. The intercalation of EG structures in clay galleries and exfoliation of clay sheets by adsorption of PVP-EG structures on clay surfaces are discussed by considering the hydrogen bonding interactions between the hydroxyl group (–OH of EG molecules, carbonyl group (C=O of PVP monomer units, and the hydroxylated aluminate surfaces of the MMT clay particles. Results suggest that the colloidal suspension of MMT clay nano particles in the PVP-EG blends provide a convenient way to obtain an electrolyte solution with tailored electrical conduction properties.

  14. Sandpile model for relaxation in complex systems

    International Nuclear Information System (INIS)

    Vazquez, A.; Sotolongo-Costa, O.; Brouers, F.

    1997-10-01

    The relaxation in complex systems is, in general, nonexponential. After an initial rapid decay the system relaxes slowly following a long time tail. In the present paper a sandpile moderation of the relaxation in complex systems is analysed. Complexity is introduced by a process of avalanches in the Bethe lattice and a feedback mechanism which leads to slower decay with increasing time. In this way, some features of relaxation in complex systems: long time tails relaxation, aging, and fractal distribution of characteristic times, are obtained by simple computer simulations. (author)

  15. 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.

  16. 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.

  17. 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....

  18. Source of non-arrhenius average relaxation time in glass-forming liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    1998-01-01

    then discuss a recently proposed model according to which the activation energy of the average relaxation time is determined by the work done in shoving aside the surrounding liquid to create space needed for a "flow event". In this model, which is based on the fact that intermolecular interactions...

  19. Postseismic relaxation process and lithospheric rheology inferred from eight years of postseismic deformation after the 2008 Mw7.9 Wenchuan earthquake

    Science.gov (United States)

    Zhao, B.; Burgmann, R.; Rui, X.; Wang, D.; Yu, J.; He, K.

    2017-12-01

    Current inferences of postseismic deformation mechanisms and lithospheric rheology in the eastern Tibetan Plateau strongly depend on spatial and temporal observations of postseismic transients following the 2008 Mw=7.9 Wenchuan earthquake. We processed regional continuously operating and survey-mode GPS data from the Crustal Movement Observation Network of China and Sichuan Continuous Operation Reference System. These data cover a broad region and time intervals of up to eight years. The determined amplitude of postseismic displacements show clear contrast between the Sichuan Basin and eastern Tibet. In addition to significant amounts of deformation in the region between the Longmen Shan and Longriba fault, reliable deformation transients are also visible in the far field, such as regions to the west of the Longriba fault and along the left-lateral Xianshuihe fault. In contrast, no more than 10 mm of postseismic transients are observed in the Sichuan Basin. Guided by previous studies, we conducted multiple-mechanism models of afterslip and viscoelastic relaxation. We first explored a series of forward viscoelastic relaxation models using a heterogeneous rheological earth structure, and then inverted corresponding afterslip distributions on the shallowly dipping detachment to explain the remaining residuals. Our preliminary results indicate the viscoelastic relaxation in the lower crust and upper mantle dominantly contributed to the mid- and far-field observations, whereas afterslip below the coseismic asperities and on small patches near the surface can explain the near-field measurements. Time-dependent slip inversions illustrate that afterslip decays more rapidly on the shallow portions of the fault interface than on the shallowly dipping detachment. Relatively long-lived right-lateral afterslip is revealed in the north segment of the Beichuan fault, suggesting variations of frictional properties along strike of the fault zone. Our results also support previous

  20. Breathing and Relaxation

    Science.gov (United States)

    ... Find a Doctor Relaxation is the absence of tension in muscle groups and a minimum or absence ... Drill Meditation Progressive Muscle Relaxation Minimizing Shortness of Breath Visualization This information has been approved by Shelby ...

  1. Relaxation property of the fractional Brownian particle

    International Nuclear Information System (INIS)

    Wang Litan; Lung, C.W.

    1988-08-01

    Dynamic susceptibility of a diffusion system associated with the fractional Brownian motion (fBm) was examined for the fractal property of the Non-Debye relaxation process. The comparisons between fBm and other approaches were made. Anomalous diffusion and the Non-Debye relaxation processes were discussed with this approach. (author). 8 refs, 1 fig

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. Proton NMR relaxation in hydrous melts

    International Nuclear Information System (INIS)

    Braunstein, J.; Bacarella, A.L.; Benjamin, B.M.; Brown, L.L.; Girard, C.

    1976-01-01

    Pulse and continuous wave NMR measurements are reported for protons in hydrous melts of calcium nitrate at temperatures between -4 and 120 0 C. Although measured in different temperature ranges, spin-lattice (T 1 ) and spin-spin (T 2 ) relaxation times appear to be nearly equal to each other and proportional to the self-diffusion coefficients of solute metal cations such as Cd 2+ . At temperatures near 50 0 C, mean Arrhenius coefficients Δ H/sub T 1 / (kcal/mol) are 7.9, 7.3, and 4.8, respectively, for melts containing 2.8, 4.0, and 8.0 moles of water per mole of calcium nitrate, compared to 4.6 kcal/mol for pure water. Temperature dependence of T 1 and T 2 in Ca(NO 3 ) 2 -2.8 H 2 O between -4 and 120 0 C are non-Arrhenius and can be represented by a Fulcher-type equation with a ''zero mobility temperature'' (T 0 ) of 225 0 K, close to the value of T 0 for solute diffusion, electrical conductance and viscosity. Resolution of the relaxation rates into correlation times for intramolecular (rotational) and intermolecular (translational) diffusional motion is discussed in terms of the Bloembergen-Purcell-Pound and more recent models for dipolar relaxation

  7. Investigation of structural relaxation, crystallization process and magnetic properties of the Fe-Ni-Si-B-C amorphous alloy

    Energy Technology Data Exchange (ETDEWEB)

    Kalezic-Glisovic, A. [Joint Laboratory for Advanced Materials of SASA, Section for Amorphous Systems, Technical Faculty Cacak, Svetog Save 65, 32000 Cacak (Serbia and Montenegro)]. E-mail: aleksandrakalezic@eunet.yu; Novakovic, L. [Faculty of Physics, Studentski trg 16, 11000 Belgrade (Serbia and Montenegro); Maricic, A. [Joint Laboratory for Advanced Materials of SASA, Section for Amorphous Systems, Technical Faculty Cacak, Svetog Save 65, 32000 Cacak (Serbia and Montenegro); Minic, D. [Faculty of Physical Chemistry, Studentski trg 16, 11000 Belgrade (Serbia and Montenegro); Mitrovic, N. [Joint Laboratory for Advanced Materials of SASA, Section for Amorphous Systems, Technical Faculty Cacak, Svetog Save 65, 32000 Cacak (Serbia and Montenegro)]. E-mail: nmitrov@tfc.kg.ac.yu

    2006-07-15

    The differential scanning calorimetry method was used for investigating the crystallization process of the Fe{sub 89.8}Ni{sub 1.5}Si{sub 5.2}B{sub 3}C{sub 0.5} amorphous alloy. It was shown that the examined alloy crystallizes in three stages. The first crystallization stage occurs at 799 K, the second at 820 K and the third at 888 K. Temperature dependence of the magnetic susceptibility relative change was investigated by the modified Faraday method in the temperature region from room temperature up to 900 K. It has been established that the Curie temperature is about 700 K for amorphous state. The magnetic susceptibility increases by 30% after the first heating up to 710 K. During the second heating up to 840 K the alloy loses its ferromagnetic features in the temperature region from 710 to 750 K, upon which it again regains the same. After the second heating magnetic susceptibility decreases by 23% as compared to the amorphous starting value and by 53% as compared to the value before the second heating. The crystallized alloy maintains ferromagnetic features in the whole temperature region during the heating up to 900 K.

  8. Investigation of structural relaxation, crystallization process and magnetic properties of the Fe-Ni-Si-B-C amorphous alloy

    International Nuclear Information System (INIS)

    Kalezic-Glisovic, A.; Novakovic, L.; Maricic, A.; Minic, D.; Mitrovic, N.

    2006-01-01

    The differential scanning calorimetry method was used for investigating the crystallization process of the Fe 89.8 Ni 1.5 Si 5.2 B 3 C 0.5 amorphous alloy. It was shown that the examined alloy crystallizes in three stages. The first crystallization stage occurs at 799 K, the second at 820 K and the third at 888 K. Temperature dependence of the magnetic susceptibility relative change was investigated by the modified Faraday method in the temperature region from room temperature up to 900 K. It has been established that the Curie temperature is about 700 K for amorphous state. The magnetic susceptibility increases by 30% after the first heating up to 710 K. During the second heating up to 840 K the alloy loses its ferromagnetic features in the temperature region from 710 to 750 K, upon which it again regains the same. After the second heating magnetic susceptibility decreases by 23% as compared to the amorphous starting value and by 53% as compared to the value before the second heating. The crystallized alloy maintains ferromagnetic features in the whole temperature region during the heating up to 900 K

  9. In vivo measurements of the T1 relaxation processes in the bone marrow in patients with myelodysplastic syndrome. A magnetic resonance imaging study

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, K.E.; Nielsen, H.; Thomsen, C.; Soerensen, P.G.; Karle, H.; Christoffersen, P.; Henriksen, O. (Hvidovre Hospital, Copenhagen (Denmark). Dept. of Magnetic Resonance; Hvidovre Hospital, Copenhagen (Denmark). Dept. of Hematology; Hvidovre Hospital, Copenhagen (Denmark). Dept. of Pathology)

    Nine patients with myelodysplastic syndrome (MDS) were examined with magnetic resonance imaging and in vivo T1 relaxation time measurements of the vertebral bone marrow in a 1.5 tesla whole body scanner. Two patients underwent transformation to acute myeloid leukemia and were evaluated at follow-up examinations. At the time of diagnosis the T1 relaxation times of the vertebral bone marrow were significantly prolonged compared with normal values. The T1 relaxation times of the vertebral bone marrow in patients with MDS showed significantly lower values compared with patients with acute leukemia and did not differ from patients with polycythemia vera. (orig.).

  10. Mechanical relaxation in glasses

    International Nuclear Information System (INIS)

    Hiki, Y.

    2004-01-01

    The basic properties of glasses and the characteristics of mechanical relaxation in glasses were briefly reviewed, and then our studies concerned were presented. Experimental methods adopted were viscosity, internal friction, ultrasonic attenuation, and Brillouin scattering measurements. The specimens used were several kinds of inorganic, organic, and metallic glasses. The measurements were mainly carried out from the room temperature up to the glass transition temperature, and the relaxation time was determined as a function of temperature. The 'double relaxation' composed of two Arrhenius-type relaxations was observed in many materials. In both relaxations, the 'compensation effect' showing a correlation of the pre-exponential factor and the activation energy was observed. These results were explained by considering the 'complex relaxation' due to cooperative motions of atoms or group of atoms. Values of activation energy near the glass transition determined by the various experimental methods were compared with each other

  11. Evaluation of PHB/Clay nanocomposite by spin-lattice relaxation time

    Directory of Open Access Journals (Sweden)

    Mariana Bruno

    2008-12-01

    Full Text Available Poly(3-hydroxybutyrate (PHB based on nanocomposites containing different amounts of a commercial organically modified clay (viscogel B7 were prepared employing solution intercalation method. Three solvents, such as: CHCl3, dimethylchloride (DMC and tetrahydrofuran (THF were used. The relationship among the processing conditions; molecular structure and intermolecular interaction, between both nanocomposite components, were investigated using a nuclear magnetic resonance (NMR, as a part of characterization methodology, which has been used by Tavares et al. It involves the hydrogen spin-lattice relaxation time, T1H, by solid state nuclear magnetic resonance, employing low field NMR. X ray diffraction was also employed because it is a conventional technique, generally used to obtain the first information on nanocomposite formation. Changes in PHB crystallinity were observed after the organophilic nanoclay had been incorporated in the polymer matrix. These changes, in the microstructure, were detected by the variation of hydrogen nuclear relaxation time values and by X ray, which showed an increase in the clay interlamelar space due to the intercalation of the polymer in the clay between lamellae. It was also observed, for both techniques, that the solvents affect directly the organization of the crystalline region, promoting a better intercalation, considering that they behave like a plasticizer.

  12. 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…

  13. 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.

  14. Dancing Crystals: A Dramatic Illustration of Intermolecular Forces

    Science.gov (United States)

    Mundell, Donald W.

    2007-01-01

    Crystals of naphthalene form on the surface of an acetone solution and dance about in an animated fashion illustrating surface tension, crystallization, and intermolecular forces. Additional experiments reveal the properties of the solution. Flows within the solutions can be visualized by various means. Previous demonstrations of surface motion…

  15. 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.

  16. Relaxation processes in rotational motion

    International Nuclear Information System (INIS)

    Broglia, R.A.

    1986-01-01

    At few MeV above the yrast line the normally strong correlations among γ-ray energies in a rotational sequence become weaker. This observation can be interpreted as evidence for the damping of rotational motion in hot nuclei. It seems possible to relate the spreading width of the E2-rotational decay strength to the spread in frequency Δω 0 of rotational bands. The origin of these fluctuations is found in: (1) fluctuations in the occupation of special single-particle orbits which contribute a significant part of the total angular momentum; and (2) fluctuations in the moment of inertia induced by vibrations of the nuclear shape. Estimates of Δω 0 done making use of the hundred-odd known discrete rotational bands in the rare-earth region lead, for moderate spin and excitation energies (I ≅ 30 and U ≅ 3 to 4 MeV), to rotational spreading widths of the order of 60 to 160 keV in overall agreement with the data. 24 refs

  17. Relaxation processes and glass transition of confined polymer melts: A molecular dynamics simulation of 1,4-polybutadiene between graphite walls.

    Science.gov (United States)

    Solar, M; Binder, K; Paul, W

    2017-05-28

    Molecular dynamics simulations of a chemically realistic model for 1,4-polybutadiene in a thin film geometry confined by two graphite walls are presented. Previous work on melts in the bulk has shown that the model faithfully reproduces static and dynamic properties of the real material over a wide temperature range. The present work studies how these properties change due to nano-confinement. The focus is on orientational correlations observable in nuclear magnetic resonance experiments and on the local intermediate incoherent neutron scattering function, F s (q z , z, t), for distances z from the graphite walls in the range of a few nanometers. Temperatures from about 2T g down to about 1.15T g , where T g is the glass transition temperature in the bulk, are studied. It is shown that weakly attractive forces between the wall atoms and the monomers suffice to effectively bind a polymer coil that is near the wall. For a wide regime of temperatures, the Arrhenius-like adsorption/desorption kinetics of the monomers is the slowest process, while very close to T g the Vogel-Fulcher-Tammann-like α-relaxation takes over. The α-process is modified only for z≤1.2 nm due to the density changes near the walls, less than expected from studies of coarse-grained (bead-spring-type) models. The weakness of the surface effects on the glass transition in this case is attributed to the interplay of density changes near the wall with the torsional potential. A brief discussion of pertinent experiments is given.

  18. Relaxation characteristics of hastelloy X

    International Nuclear Information System (INIS)

    Suzuki, Kazuhiko

    1980-02-01

    Relaxation diagrams of Hastelloy X (relaxation curves, relaxation design diagrams, etc.) were generated from the creep constitutive equation of Hastelloy X, using inelastic stress analysis code TEPICC-J. These data are in good agreement with experimental relaxation data of ORNL-5479. Three typical inelastic stress analyses were performed for various relaxation behaviors of the high-temperature structures. An attempt was also made to predict these relaxation behaviors by the relaxation curves. (author)

  19. TEACHING NEUROMUSCULAR RELAXATION.

    Science.gov (United States)

    NORRIS, JEANNE E.; STEINHAUS, ARTHUR H.

    THIS STUDY ATTEMPTED TO FIND OUT WHETHER (1) THE METHODS FOR ATTAINING NEUROMUSCULAR RELAXATION THAT HAVE PROVED FRUITFUL IN THE ONE-TO-ONE RELATIONSHIP OF THE CLINIC CAN BE SUCCESSFULLY ADAPTED TO THE TEACHER-CLASS RELATIONSHIP OF THE CLASSROOM AND GYMNASIUM, AND (2) NEUROMUSCULAR RELAXATION CAN BE TAUGHT SUCCESSFULLY BY AN APPROPRIATELY TRAINED…

  20. Relaxation of Anisotropic Glasses

    DEFF Research Database (Denmark)

    Deubener, Joachim; Martin, Birgit; Wondraczek, Lothar

    2004-01-01

    . When the load was removed at room temperature a permanent optical anisotropy (birefringence) was observed only perpendicular to cylinder axis and the pressure direction indicating complete elimination of thermal stresses. Relaxation of structural anisotropy was studied from reheating experiments using...... the energy release, thermo-mechanical and optical relaxation behaviour are drawn....

  1. Relaxation techniques for stress

    Science.gov (United States)

    ... raise your heart rate. This is called the stress response. Relaxation techniques can help your body relax and lower your blood pressure ... also many other types of breathing techniques you can learn. In many cases, you do not need much ... including those that cause stress. Meditation has been practiced for thousands of years, ...

  2. Spin-lattice relaxation in phosphorescent triplet state molecules

    International Nuclear Information System (INIS)

    Verbeek, P.J.F.

    1979-01-01

    The present thesis contains the results of a study of spin-lattice relaxation (SLR) in the photo-excited triplet state of aromatic molecules, dissolved in a molecular host crystal. It appears that SLR in phosphorescent triplet state molecules often is related to the presence of so-called (pseudo) localized phonons in the molecular mixed crystals. These local phonons can be thought to correspond with vibrations (librations) of the guest molecule in the force field of the surrounding host molecules. Since the intermolecular forces are relatively weak, the frequencies corresponding with these vibrations are relatively low and usually are of the order of 10-30 cm -1 . (Auth.)

  3. High signal to noise ratio THz spectroscopy with ASOPS and signal processing schemes for mapping and controlling molecular and bulk relaxation processes

    International Nuclear Information System (INIS)

    Hadjiloucas, S; Walker, G C; Bowen, J W; Becerra, V M; Zafiropoulos, A; Galvao, R K H

    2009-01-01

    Asynchronous Optical Sampling has the potential to improve signal to noise ratio in THz transient sperctrometry. The design of an inexpensive control scheme for synchronising two femtosecond pulse frequency comb generators at an offset frequency of 20 kHz is discussed. The suitability of a range of signal processing schemes adopted from the Systems Identification and Control Theory community for further processing recorded THz transients in the time and frequency domain are outlined. Finally, possibilities for femtosecond pulse shaping using genetic algorithms are mentioned.

  4. High signal to noise ratio THz spectroscopy with ASOPS and signal processing schemes for mapping and controlling molecular and bulk relaxation processes

    Energy Technology Data Exchange (ETDEWEB)

    Hadjiloucas, S; Walker, G C; Bowen, J W; Becerra, V M [Cybernetics, School of Systems Engineering, University of Reading, RG6 6AY (United Kingdom); Zafiropoulos, A [Biosystems Engineering Department, School of Agricultural Technology, Technological Educational Institute of Larissa, 411 10, Larissa (Greece); Galvao, R K H, E-mail: s.hadjiloucas@reading.ac.u [Divisao de Engenharia Eletronica, Instituto Tecnologico de Aeronautica, Sao Jose dos Campos, SP, 12228-900 Brazil (Brazil)

    2009-08-01

    Asynchronous Optical Sampling has the potential to improve signal to noise ratio in THz transient sperctrometry. The design of an inexpensive control scheme for synchronising two femtosecond pulse frequency comb generators at an offset frequency of 20 kHz is discussed. The suitability of a range of signal processing schemes adopted from the Systems Identification and Control Theory community for further processing recorded THz transients in the time and frequency domain are outlined. Finally, possibilities for femtosecond pulse shaping using genetic algorithms are mentioned.

  5. Stress relaxation under cyclic electron irradiation

    International Nuclear Information System (INIS)

    Bystrov, L.N.; Reznitskij, M.E.

    1990-01-01

    The kinetics of deformation process in a relaxating sample under 2 MeV electron cyclic irradiation was studied experimentally. The Al-Mg alloys with controllable and different (in dislocation density precipitate presence and their character) structure were used in experiments. It was established that after the beam was switched on the deformation rate increased sharply and then, during prolonged irradiation, in a gradual manner. After the switching-off the relaxation rate decreases by jumps up to values close to extrapolated rates of pre-radiation relaxation. The exhibition of these effects with radiation switching-off and switchin-on is dependent on the initial rate of thermal relaxation, the test temperature, the preliminary cold deformation and the dominating deformation dislocation mechanism. The preliminary cold deformation and test temperature elevation slightly decrease the effect of instantaneous relaxation acceleration with the irradiation switch-on. 17 refs., 5 figs

  6. Nuclear spin phonon relaxation by Raman process in Na{sub 3}H(SO{sub 4}){sub 2} single crystals with the electric-quadrupole-type interaction using {sup 1}H and {sup 23}Na NMR

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Ae Ran [Department of Science Education, Jeonju University, Jeonju 560-759, Chonbuk (Korea, Republic of)], E-mail: aeranlim@hanmail.net; Shin, Chang Woo [Solid State Analysis Team, Korea Basic Science Institute, Daegu 702-701 (Korea, Republic of)

    2008-11-30

    Successive phase transitions in a Na{sub 3}H(SO{sub 4}){sub 2} single crystal were found at 296, 513, and 533 K. To investigate the mechanism of the phase transition at 296 K, the {sup 1}H and {sup 23}Na spin-lattice relaxation time and the spin-spin relaxation time of Na{sub 3}H(SO{sub 4}){sub 2} were measured near the phase transition temperature using a FT NMR spectrometer. The spin-lattice relaxation time, T{sub 1}, for {sup 1}H in Na{sub 3}H(SO{sub 4}){sub 2} crystals exhibits a minimum below T{sub C1} (=296 K) indicating the presence of distinct molecular motion governed by the Bloembergen-Purcell-Pound (BPP) theory. Although the results for the {sup 1}H and {sup 23}Na relaxation times provide no evidence of the phase transition at T{sub C1}, the separation of the {sup 23}Na resonance lines changes abruptly at T{sub C1}. The phase transition at 296 K produces a change in the separation of the Na resonance line that is associated with a change in the atomic positions in the vicinity of the Na ions. Also, the nuclear spin-lattice relaxation process in Na{sub 3}H(SO{sub 4}){sub 2} crystals with the electric-quadrupole-type interaction proceed via Raman process. These results are compared with those obtained for other M{sub 3}H(SO{sub 4}){sub 2} (M=K, Rb, and Cs) crystals, which have similar hydrogen-bonded structures.

  7. Simultaneous spectral and temporal analyses of kinetic energies in nonequilibrium systems: theory and application to vibrational relaxation of O-D stretch mode of HOD in water.

    Science.gov (United States)

    Jeon, Jonggu; Lim, Joon Hyung; Kim, Seongheun; Kim, Heejae; Cho, Minhaeng

    2015-05-28

    A time series of kinetic energies (KE) from classical molecular dynamics (MD) simulation contains fundamental information on system dynamics. It can also be analyzed in the frequency domain through Fourier transformation (FT) of velocity correlation functions, providing energy content of different spectral regions. By limiting the FT time span, we have previously shown that spectral resolution of KE evolution is possible in the nonequilibrium situations [Jeon and Cho, J. Chem. Phys. 2011, 135, 214504]. In this paper, we refine the method by employing the concept of instantaneous power spectra, extending it to reflect an instantaneous time-correlation of velocities with those in the future as well as with those in the past, and present a new method to obtain the instantaneous spectral density of KE (iKESD). This approach enables the simultaneous spectral and temporal resolution of KE with unlimited time precision. We discuss the formal and novel properties of the new iKESD approaches and how to optimize computational methods and determine parameters for practical applications. The method is specifically applied to the nonequilibrium MD simulation of vibrational relaxation of the OD stretch mode in a hydrated HOD molecule by employing a hybrid quantum mechanical/molecular mechanical (QM/MM) potential. We directly compare the computational results with the OD band population relaxation time profiles extracted from the IR pump-probe measurements for 5% HOD in water. The calculated iKESD yields the OD bond relaxation time scale ∼30% larger than the experimental value, and this decay is largely frequency-independent if the classical anharmonicity is accounted for. From the integrated iKESD over intra- and intermolecular bands, the major energy transfer pathways were found to involve the HOD bending mode in the subps range, then the internal modes of the solvent until 5 ps after excitation, and eventually the solvent intermolecular modes. Also, strong hydrogen

  8. Intermolecular Hydrogen Transfer in Isobutane Hydrate

    Directory of Open Access Journals (Sweden)

    Takeshi Sugahara

    2012-05-01

    Full Text Available Electron spin resonance (ESR spectra of butyl radicals induced with γ-ray irradiation in the simple isobutane (2-methylpropane hydrate (prepared with deuterated water were investigated. Isothermal annealing results of the γ-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol of hydrogen picking in the γ-ray-irradiated propane hydrate with deuterated water.

  9. F19 relaxation in non-magnetic hexafluorides

    International Nuclear Information System (INIS)

    Rigny, P.

    1969-01-01

    The interesting properties of the fluorine magnetic resonance in the hexafluorides of molybdenum, tungsten and uranium, are very much due to large anisotropies of the chemical shift tensors. In the solid phases these anisotropies, the values of which are deduced from line shape studies, allow one to show that the molecules undergo hindered rotations about the metal atom. The temperature and frequency dependence of the fluorine longitudinal relaxation times shows that the relaxation is due to the molecular motion. The dynamical parameters of this motion are then deduced from the complete study of the fluorine relaxation in the rotating frame. In the liquid phases, the existence of anisotropies allows an estimation of the different contributions to the relaxation. In particular, the frequency and temperature dependence of the relaxation shows it to be dominated by the spin-rotation interaction. We have shown that the strength of this interaction can be deduced from the chemical shifts, and the angle through which the molecule rotates quasi-freely can be determined. In the hexafluorides, this angle is roughly one radian at 70 C, and with the help of this value, the friction coefficients which describe the intermolecular interactions are discussed. (author) [fr

  10. The relaxation time approximation

    International Nuclear Information System (INIS)

    Gairola, R.P.; Indu, B.D.

    1991-01-01

    A plausible approximation has been made to estimate the relaxation time from a knowledge of the transition probability of phonons from one state (r vector, q vector) to other state (r' vector, q' vector), as a result of collision. The relaxation time, thus obtained, shows a strong dependence on temperature and weak dependence on the wave vector. In view of this dependence, relaxation time has been expressed in terms of a temperature Taylor's series in the first Brillouin zone. Consequently, a simple model for estimating the thermal conductivity is suggested. the calculations become much easier than the Callaway model. (author). 14 refs

  11. In vivo measurements of the T1 relaxation processes in the bone marrow in patients with myelodysplastic syndrome. A magnetic resonance imaging study

    DEFF Research Database (Denmark)

    Jensen, K E; Nielsen, H; Thomsen, C

    1989-01-01

    Nine patients with myelodysplastic syndrome (MDS) were examined with magnetic resonance imaging and in vivo T1 relaxation time measurements of the vertebral bone marrow in a 1.5 tesla whole body scanner. Two patients underwent transformation to acute myeloid leukemia and were evaluated at follow-...... not differ from patients with polycythemia vera....

  12. Changes in T1 relaxation processes in the bone marrow following treatment in children with acute lymphoblastic leukemia. A magnetic resonance imaging study

    DEFF Research Database (Denmark)

    Jensen, K E; Thomsen, C; Henriksen, O

    1990-01-01

    data from bone marrow biopsies obtained in close association to the MR examinations. Ten age matched children were examined as a control group. A 1.5 Tesla whole body scanner was used for the measurements. The pretreatment T1 relaxation times of the bone marrow were significantly prolonged, compared...

  13. 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

  14. 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.

  15. 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.

  16. Nuclear magnetic resonance relaxation in multiple sclerosis

    DEFF Research Database (Denmark)

    Larsson, H B; Barker, G J; MacKay, A

    1998-01-01

    OBJECTIVES: The theory of relaxation processes and their measurements are described. An overview is presented of the literature on relaxation time measurements in the normal and the developing brain, in experimental diseases in animals, and in patients with multiple sclerosis. RESULTS...... AND CONCLUSION: Relaxation time measurements provide insight into development of multiple sclerosis plaques, especially the occurrence of oedema, demyelination, and gliosis. There is also evidence that normal appearing white matter in patients with multiple sclerosis is affected. What is now needed are fast...

  17. Relaxation and hypnosis in pediatric dental patients.

    Science.gov (United States)

    Peretz, B

    1996-01-01

    Relaxation and hypnosis are methods which, may solve the problem of extreme dental anxiety, when all other methods, behavioral or pharmacological may not be used. A simple definition of hypnosis is suggestion and repetition. Suggestion is the process whereby an individual accepts a proposition put to him by another, without having the slightest logical reason for doing so. Relaxation is one method of inducing hypnosis. A case of using hypnosis on an 11-year-old boy is described.

  18. Regularities of intermediate adsorption complex relaxation

    International Nuclear Information System (INIS)

    Manukova, L.A.

    1982-01-01

    The experimental data, characterizing the regularities of intermediate adsorption complex relaxation in the polycrystalline Mo-N 2 system at 77 K are given. The method of molecular beam has been used in the investigation. The analytical expressions of change regularity in the relaxation process of full and specific rates - of transition from intermediate state into ''non-reversible'', of desorption into the gas phase and accumUlation of the particles in the intermediate state are obtained

  19. Arresting relaxation in Pickering Emulsions

    Science.gov (United States)

    Atherton, Tim; Burke, Chris

    2015-03-01

    Pickering emulsions consist of droplets of one fluid dispersed in a host fluid and stabilized by colloidal particles absorbed at the fluid-fluid interface. Everyday materials such as crude oil and food products like salad dressing are examples of these materials. Particles can stabilize non spherical droplet shapes in these emulsions through the following sequence: first, an isolated droplet is deformed, e.g. by an electric field, increasing the surface area above the equilibrium value; additional particles are then adsorbed to the interface reducing the surface tension. The droplet is then allowed to relax toward a sphere. If more particles were adsorbed than can be accommodated by the surface area of the spherical ground state, relaxation of the droplet is arrested at some non-spherical shape. Because the energetic cost of removing adsorbed colloids exceeds the interfacial driving force, these configurations can remain stable over long timescales. In this presentation, we present a computational study of the ordering present in anisotropic droplets produced through the mechanism of arrested relaxation and discuss the interplay between the geometry of the droplet, the dynamical process that produced it, and the structure of the defects observed.

  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. Dielectric dispersion, relaxation dynamics and thermodynamic studies of Beta-Alanine in aqueous solutions using picoseconds time domain reflectometry

    Science.gov (United States)

    Vinoth, K.; Ganesh, T.; Senthilkumar, P.; Sylvester, M. Maria; Karunakaran, D. J. S. Anand; Hudge, Praveen; Kumbharkhane, A. C.

    2017-09-01

    The aqueous solution of beta-alanine characterised and studied by their dispersive dielectric properties and relaxation process in the frequency domain of 10×106 Hz to 30×109 Hz with varying concentration in mole fractions and temperatures. The molecular interaction and dielectric parameters are discussed in terms of counter-ion concentration theory. The static permittivity (ε0), high frequency dielectric permittivity (ε∞) and excess dielectric parameters are accomplished by frequency depended physical properties and relaxation time (τ). Molecular orientation, ordering and correlation factors are reported as confirmation of intermolecular interactions. Ionic conductivity and thermo dynamical properties are concluded with the behaviour of the mixture constituents. Solute-solvent, solute-solute interaction, structure making and breaking abilities of the solute in aqueous medium are interpreted. Fourier Transform Infrared (FTIR) spectra of beta- alanine single crystal and liquid state have been studied. The 13C Nuclear Magnetic Resonance (NMR) spectral studies give the signature for resonating frequencies and chemical shifts of beta-alanine.

  2. 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.

  3. 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.

  4. 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.

  5. Relaxation strain measurements in cellular dislocation structures

    International Nuclear Information System (INIS)

    Tsai, C.Y.; Quesnel, D.J.

    1984-01-01

    The conventional picture of what happens during a stress relaxation usually involves imagining the response of a single dislocation to a steadily decreasing stress. The velocity of this dislocation decreases with decreasing stress in such a way that we can measure the stress dependence of the dislocation velocity. Analysis of the data from a different viewpoint enables us to calculate the apparent activation volume for the motion of the dislocation under the assumption of thermally activated glie. Conventional thinking about stress relaxation, however, does not consider the eventual fate of this dislocation. If the stress relaxes to a low enough level, it is clear that the dislocation must stop. This is consistent with the idea that we can determine the stress dependence of the dislocation velocity from relaxation data only for those cases where the dislocation's velocity is allowed to approach zero asymptotically, in short, for those cases where the dislocation never stops. This conflict poses a dilemma for the experimentalist. In real crystals, however, obstacles impede the dislocation's progress so that those dislocations which are stopped at a given stress will probably never resume motion under the influence of the steadily declining stress present during relaxation. Thus one could envision stress relaxation as a process of exhaustion of mobile dislocations, rather than a process of decreasing dislocation velocity. Clearly both points of view have merit and in reality both mechanisms contribute to the phenomena

  6. Relaxation of quadrupole orientation in an optically pumped alkali vapour

    Energy Technology Data Exchange (ETDEWEB)

    Bernabeu, E; Tornos, J

    1985-04-01

    The relaxation of quadrupole orientation (alignment) in an optically pumped alkali vapour is theoretically studied by taking into account the relaxation processes by alkali-buffer gas, alkali-alkali with spin exchange and alkali-cell wall (diffusion process) collisions. The relaxation transients of the quadrupole orientation are obtained by introducing a first-order weak-pumping approximation (intermediate pumping) less restrictive than the usually considered (zeroth order) one.

  7. 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.

  8. Magneto-dependent stress relaxation of magnetorheological gels

    KAUST Repository

    Xu, Yangguang; Liu, Taixiang; Liao, G J; Lubineau, Gilles

    2017-01-01

    The stress relaxation behaviors of magnetorheological (MR) gels under stepwise shear loading are systematically investigated. The particle-enhanced effect, the magneto-induced effect, and the temperature-enhanced effect on the stress relaxation of MR gels are discussed. For further analysis of the magneto-induced stress relaxation mechanism in MR gels, a phenomenological model is established to describe the stress relaxation behavior of the matrix and the magnetic particle chains. All characteristic parameters introduced in the model, i.e. relaxation time, instantaneous modulus, and stable modulus, have well-defined physical meanings and are fitted based on the experimental results. The influence of each parameter on the macroscopic response is discussed and it is found that the relaxation stress induced by the magneto-mechanical coupling effect plays an important role in the stress relaxation process of MR gels.

  9. Magneto-dependent stress relaxation of magnetorheological gels

    KAUST Repository

    Xu, Yangguang

    2017-09-01

    The stress relaxation behaviors of magnetorheological (MR) gels under stepwise shear loading are systematically investigated. The particle-enhanced effect, the magneto-induced effect, and the temperature-enhanced effect on the stress relaxation of MR gels are discussed. For further analysis of the magneto-induced stress relaxation mechanism in MR gels, a phenomenological model is established to describe the stress relaxation behavior of the matrix and the magnetic particle chains. All characteristic parameters introduced in the model, i.e. relaxation time, instantaneous modulus, and stable modulus, have well-defined physical meanings and are fitted based on the experimental results. The influence of each parameter on the macroscopic response is discussed and it is found that the relaxation stress induced by the magneto-mechanical coupling effect plays an important role in the stress relaxation process of MR gels.

  10. Relaxed Binaural LCMV Beamforming

    NARCIS (Netherlands)

    Koutrouvelis, A.; Hendriks, R.C.; Heusdens, R.; Jensen, Jesper Rindom

    2017-01-01

    In this paper, we propose a new binaural beamforming technique, which can be seen as a relaxation of the linearly constrained minimum variance (LCMV) framework. The proposed method can achieve simultaneous noise reduction and exact binaural cue preservation of the target source, similar to the

  11. Influence of silver nanoparticles on relaxation processes and efficiency of dipole – dipole energy transfer between dye molecules in polymethylmethacrylate films

    Energy Technology Data Exchange (ETDEWEB)

    Bryukhanov, V V; Borkunov, R Yu; Tsarkov, M V [Immanuel Kant Baltic Federal University, Kaliningrad (Russian Federation); Konstantinova, E I; Slezhkin, V A [Kaliningrad State Technical University, Kaliningrad (Russian Federation)

    2015-10-31

    The fluorescence and phosphorescence of dyes in thin polymethylmethacrylate (PMMA) films in the presence of ablated silver nanoparticles has been investigated in a wide temperature range by methods of femtosecond and picosecond laser photoexcitation. The fluorescence and phosphorescence times, as well as spectral and kinetic characteristics of rhodamine 6G (R6G) molecules in PMMA films are measured in a temperature range of 80 – 330 K. The temperature quenching activation energy of the fluorescence of R6G molecules in the presence of ablated silver nanoparticles is found. The vibrational relaxation rate of R6G in PMMA films is estimated, the efficiency of the dipole – dipole electron energy transfer between R6G and brilliant green molecules (enhanced by plasmonic interaction with ablated silver nanoparticles) is analysed, and the constants of this energy transfer are determined. (nanophotonics)

  12. Influence of silver nanoparticles on relaxation processes and efficiency of dipole – dipole energy transfer between dye molecules in polymethylmethacrylate films

    International Nuclear Information System (INIS)

    Bryukhanov, V V; Borkunov, R Yu; Tsarkov, M V; Konstantinova, E I; Slezhkin, V A

    2015-01-01

    The fluorescence and phosphorescence of dyes in thin polymethylmethacrylate (PMMA) films in the presence of ablated silver nanoparticles has been investigated in a wide temperature range by methods of femtosecond and picosecond laser photoexcitation. The fluorescence and phosphorescence times, as well as spectral and kinetic characteristics of rhodamine 6G (R6G) molecules in PMMA films are measured in a temperature range of 80 – 330 K. The temperature quenching activation energy of the fluorescence of R6G molecules in the presence of ablated silver nanoparticles is found. The vibrational relaxation rate of R6G in PMMA films is estimated, the efficiency of the dipole – dipole electron energy transfer between R6G and brilliant green molecules (enhanced by plasmonic interaction with ablated silver nanoparticles) is analysed, and the constants of this energy transfer are determined. (nanophotonics)

  13. 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.

  14. 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

  15. 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)

  16. Hair Dye and Hair Relaxers

    Science.gov (United States)

    ... For Consumers Consumer Information by Audience For Women Hair Dye and Hair Relaxers Share Tweet Linkedin Pin it More sharing ... products. If you have a bad reaction to hair dyes and relaxers, you should: Stop using the ...

  17. Relaxation Time of High-Density Amorphous Ice

    Science.gov (United States)

    Handle, Philip H.; Seidl, Markus; Loerting, Thomas

    2012-06-01

    Amorphous water plays a fundamental role in astrophysics, cryoelectron microscopy, hydration of matter, and our understanding of anomalous liquid water properties. Yet, the characteristics of the relaxation processes taking place in high-density amorphous ice (HDA) are unknown. We here reveal that the relaxation processes in HDA at 110-135 K at 0.1-0.2 GPa are of collective and global nature, resembling the alpha relaxation in glassy material. Measured relaxation times suggest liquid-like relaxation characteristics in the vicinity of the crystallization temperature at 145 K. By carefully relaxing pressurized HDA for several hours at 135 K, we produce a state that is closer to the ideal glass state than all HDA states discussed so far in literature.

  18. Cross-relaxation in multiple pulse NQR spin-locking

    Energy Technology Data Exchange (ETDEWEB)

    Beltjukov, P. A.; Kibrik, G. E. [Perm State University, Physics Department (Russian Federation); Furman, G. B., E-mail: gregoryf@bgu.ac.il; Goren, S. D. [Ben Gurion University, Physics Department (Israel)

    2008-01-15

    The experimental and theoretical NQR multiple-pulse spin locking study of cross-relaxation process in solids containing nuclei of two different sorts I > 1/2 and S = 1/2 coupled by the dipole-dipole interactions and influenced by an external magnetic field. Two coupled equations for the inverse spin temperatures of the both spin systems describing the mutual spin lattice relaxation and the cross-relaxation were obtained using the method of the nonequilibrium state operator. It is shown that the relaxation process is realized with non-exponential time dependence describing by a sum of two exponents. The cross relaxation time is calculated as a function of the multiple-pulse field parameters which agree with the experimental data. The calculated magnetization cross relaxation time vs the strength of the applied magnetic field agrees well with the obtained experimental data.

  19. Experiments in paramagnetic relaxation

    International Nuclear Information System (INIS)

    Lijphart, E.E.

    1976-01-01

    This thesis presents two attempts to improve the resolving power of the relaxation measurement technique. The first attempt reconsiders the old technique of steady state saturation. When used in conjunction with the pulse technique, it offers the possibility of obtaining additional information about the system in which all-time derivatives are zero; in addition, non-linear effects may be distinguished from each other. The second attempt involved a systematic study of only one system: Cu in the Tutton salts (K and Rb). The systematic approach, the high accuracy of the measurement and the sheer amount of experimental data for varying temperature, magnetic field and concentration made it possible in this case to separate the prevailing relaxation mechanisms reliably

  20. 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

  1. 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)

  2. Relaxation from particle production

    Energy Technology Data Exchange (ETDEWEB)

    Hook, Anson; Marques-Tavares, Gustavo [Stanford Institute for Theoretical Physics, Stanford University, Stanford, CA 94305 (United States)

    2016-12-20

    We consider using particle production as a friction force by which to implement a “Relaxion” solution to the electroweak hierarchy problem. Using this approach, we are able to avoid superplanckian field excursions and avoid any conflict with the strong CP problem. The relaxation mechanism can work before, during or after inflation allowing for inflationary dynamics to play an important role or to be completely decoupled.

  3. 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

  4. Magnetic relaxation in anisotropic magnets

    DEFF Research Database (Denmark)

    Lindgård, Per-Anker

    1971-01-01

    The line shape and the kinematic and thermodynamic slowing down of the critical and paramagnetic relaxation in axially anisotropic materials are discussed. Kinematic slowing down occurs only in the longitudinal relaxation function. The thermodynamic slowing down occurs in either the transverse...... or longitudinal relaxation function depending on the sign of the axial anisotropy....

  5. Momentum constraint relaxation

    International Nuclear Information System (INIS)

    Marronetti, Pedro

    2006-01-01

    Full relativistic simulations in three dimensions invariably develop runaway modes that grow exponentially and are accompanied by violations of the Hamiltonian and momentum constraints. Recently, we introduced a numerical method (Hamiltonian relaxation) that greatly reduces the Hamiltonian constraint violation and helps improve the quality of the numerical model. We present here a method that controls the violation of the momentum constraint. The method is based on the addition of a longitudinal component to the traceless extrinsic curvature A ij -tilde, generated by a vector potential w i , as outlined by York. The components of w i are relaxed to solve approximately the momentum constraint equations, slowly pushing the evolution towards the space of solutions of the constraint equations. We test this method with simulations of binary neutron stars in circular orbits and show that it effectively controls the growth of the aforementioned violations. We also show that a full numerical enforcement of the constraints, as opposed to the gentle correction of the momentum relaxation scheme, results in the development of instabilities that stop the runs shortly

  6. 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.

  7. Excited-state relaxation of some aminoquinolines

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available The absorption and fluorescence spectra, fluorescence quantum yields and lifetimes, and fluorescence rate constants ( k f of 2-amino-3-( 2 ′ -benzoxazolylquinoline (I, 2-amino-3-( 2 ′ -benzothiazolylquinoline (II, 2-amino-3-( 2 ′ -methoxybenzothiazolyl-quinoline (III, 2-amino-3-( 2 ′ -benzothiazolylbenzoquinoline (IV at different temperatures have been measured. The shortwavelength shift of fluorescence spectra of compounds studied (23–49 nm in ethanol as the temperature decreases (the solvent viscosity increases points out that the excited-state relaxation process takes place. The rate of this process depends essentially on the solvent viscosity, but not the solvent polarity. The essential increasing of fluorescence rate constant k f (up to about 7 times as the solvent viscosity increases proves the existence of excited-state structural relaxation consisting in the mutual internal rotation of molecular fragments of aminoquinolines studied, followed by the solvent orientational relaxation.

  8. Momentum and mass relaxation in heavy-ion collisions

    International Nuclear Information System (INIS)

    Gregoire, C.; Scheuter, F.; Remaud, B.; Sebille, F.

    1984-01-01

    The momentum and mass relaxation are shown to be described by transport equations. The momentum relaxation, which can be studied in the intermediate energy regime by the particle emissions, refers to a microscopic slowing down and diffusion process in the momentum space. The mass relaxation refers to the coupling of the collective mass asymmetry degree of freedom and the intrinsic system. It can be illustrated by the fast fission of light and very heavy systems

  9. 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.

  10. Vogel-Fulcher dependence of relaxation rates in a nematic monomer and elastomer

    Science.gov (United States)

    Shenoy, D.; Filippov, S.; Aliev, F.; Keller, P.; Thomsen, D.; Ratna, B.

    2000-12-01

    Dielectric relaxation spectroscopy is used to study the relaxation processes in a nematic monomer and the corresponding cross-linked polymer nematic liquid crystal (elastomer). In the frequency window 10 mHz to 2 GHz the monomer liquid crystal shows a single relaxation whereas the polymer exhibits three relaxation processes, two of which are quantitatively analyzed. The temperature dependence of relaxation times in both the monomer and polymer follows a Vogel-Fulcher behavior. The relaxation processes are identified with specific molecular motions and activation energies are calculated in a linear approximation for comparison with literature data.

  11. Interaction of iron with boron in metal-rich metallaboranes resulting in large deshielding and rapid relaxation processes of the boron-11 nucleus

    International Nuclear Information System (INIS)

    Rath, N.P.; Fehlner, T.P.

    1988-01-01

    A first-order, parameterized model for calculating 11 B chemical shifts in metal-rich ferraboranes and a correlation of chemical shift with boron Mulliken populations from Fenske-Hall calculations are presented. These correlations are qualitatively different from those reported earlier for boranes and suggest that direct iron-boron interactions lead to large deshielding due to substantial increases in multiple-bond contributions to the shielding tensor. Relaxation rates have been measured for [Fe 4 (CO) 12 BH/sub 3-n/]/sup n-/ (n = 0-2) and correlated with electric field gradients at the boron nucleus estimated from Fenske-Hall calculations. These results demonstrate that formation of the boride, [Fe 4 (CO) 12 B] 3- , by deprotonation is accompanied by the development of large asymmetries in the electronic charge distribution around the boron nucleus. Finally, 7 Li NMR is used to probe the nature of the anions [Fe 4 (CO) 12 BH/sub 3-n/]/sup n-/ (n = 1-3), and observed line shapes suggest close association of Li + with the trianion. 28 references, 3 figures, 4 tables

  12. Nuclear magnetic relaxation by the dipolar EMOR mechanism: Multi-spin systems

    Science.gov (United States)

    Chang, Zhiwei; Halle, Bertil

    2017-08-01

    In aqueous systems with immobilized macromolecules, including biological tissues, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. Starting from the stochastic Liouville equation, we have previously developed a rigorous EMOR relaxation theory for dipole-coupled two-spin and three-spin systems. Here, we extend the stochastic Liouville theory to four-spin systems and use these exact results as a guide for constructing an approximate multi-spin theory, valid for spin systems of arbitrary size. This so-called generalized stochastic Redfield equation (GSRE) theory includes the effects of longitudinal-transverse cross-mode relaxation, which gives rise to an inverted step in the relaxation dispersion profile, and coherent spin mode transfer among solid-like spins, which may be regarded as generalized spin diffusion. The GSRE theory is compared to an existing theory, based on the extended Solomon equations, which does not incorporate these phenomena. Relaxation dispersion profiles are computed from the GSRE theory for systems of up to 16 protons, taken from protein crystal structures. These profiles span the range from the motional narrowing limit, where the coherent mode transfer plays a major role, to the ultra-slow motion limit, where the zero-field rate is closely related to the strong-collision limit of the dipolar relaxation rate. Although a quantitative analysis of experimental data is beyond the scope of this work, it is clear from the magnitude of the predicted relaxation rate and the shape of the relaxation dispersion profile that the dipolar EMOR mechanism is the principal cause of water-1H low-field longitudinal relaxation in aqueous systems of immobilized macromolecules, including soft biological tissues. The relaxation theory developed here therefore provides a basis for molecular-level interpretation of endogenous soft

  13. Spin relaxation of iron in mixed state hemoproteins

    International Nuclear Information System (INIS)

    Wajnberg, E.; Kalinowski, H.J.; Bemski, G.; Helman, J.S.

    1984-01-01

    In pure states hemoproteins the relaxation of iron depends on its spin state. It is found that in both mixed state met-hemoglobin and met-myoglobin, the low and high spin states relax through an Orbach-like process. Also, very short (approx. 1 ns) and temperature independent transverse relaxation times T 2 were estimated. This peculiar behaviour of the relaxation may result from the unusual electronic structure of mixed state hemoproteins that allows thermal equilibrium and interconversion of the spin states. (Author) [pt

  14. Green--Kubo formula for collisional relaxation

    International Nuclear Information System (INIS)

    Visscher, P.B.

    1988-01-01

    In this paper we generalize the Green--Kubo method (usually used for obtaining formulas for transport coefficients involving conserved densities) to relaxation processes occurring during collisions, such as the transfer of energy from vibrational to translational modes in a molecular fluid. We show that the relaxation rate can be calculated without evaluating time correlation functions over long times, and can in fact be written as a sum over collisions which makes the relation between the Green--Kubo method and approximate independent-collision models much clearer

  15. Simulation study of stepwise relaxation in a spheromak plasma

    International Nuclear Information System (INIS)

    Horiuchi, Ritoku; Uchida, Masaya; Sato, Tetsuya.

    1991-10-01

    The energy relaxation process of a spheromak plasma in a flux conserver is investigated by means of a three-dimensional magnetohydrodynamic simulation. The resistive decay of an initial force-free profile brings the spheromak plasma to an m = 1/n = 2 ideal kink unstable region. It is found that the energy relaxation takes place in two steps; namely, the relaxation consists of two physically distinguished phases, and there exists an intermediate phase in between, during which the relaxation becomes inactive temporarily. The first relaxation corresponds to the transition from an axially symmetric force-free state to a helically symmetric one with an n = 2 crescent magnetic island structure via the helical kink instability. The n = 2 helical structure is nonlinearly sustained in the intermediate phase. The helical twisting of the flux tube creates a reconnection current in the vicinity of the geometrical axis. The second relaxation is triggered by the rapid growth of the n = 1 mode when the reconnection current exceeds a critical value. The helical twisting relaxes through magnetic reconnection toward an axially symmetric force-free state. It is also found that the poloidal flux reduces during the helical twisting in the first relaxation and the generation of the toroidal flux occurs through the magnetic reconnection process in the second relaxation. (author)

  16. Waveform relaxation methods for implicit differential equations

    NARCIS (Netherlands)

    P.J. van der Houwen; W.A. van der Veen

    1996-01-01

    textabstractWe apply a Runge-Kutta-based waveform relaxation method to initial-value problems for implicit differential equations. In the implementation of such methods, a sequence of nonlinear systems has to be solved iteratively in each step of the integration process. The size of these systems

  17. Muon spin relaxation in ferromagnets. Pt. 1

    International Nuclear Information System (INIS)

    Lovesey, S.W.; Karlsson, E.B.

    1991-04-01

    Expressions for the dipolar and hyperfine contributions to the relaxation rate of muons implanted in a ferromagnet are presented and analysed using the Heisenberg model of spin-waves including dipolar and Zeeman energies. Calculations for EuO indicate that relaxation is likely to be dominated by the hyperfine mechanism, even if the ratio of the hyperfine and dipolar coupling constants is small. The hyperfine mechanism is sensitive to the dipolar energy of the atomic spins, whereas the dipolar mechanisms depend essentially on the exchange energy. For both mechanisms there is an almost quadratic dependence on temperature, throughout much of the ordered magnetic phase, which reflects two-spin-wave difference events from the Raman-type relaxation processes. (author)

  18. Variational formulation of relaxed and multi-region relaxed magnetohydrodynamics

    Science.gov (United States)

    Dewar, R. L.; Yoshida, Z.; Bhattacharjee, A.; Hudson, S. R.

    2015-12-01

    > Ideal magnetohydrodynamics (IMHD) is strongly constrained by an infinite number of microscopic constraints expressing mass, entropy and magnetic flux conservation in each infinitesimal fluid element, the latter preventing magnetic reconnection. By contrast, in the Taylor relaxation model for formation of macroscopically self-organized plasma equilibrium states, all these constraints are relaxed save for the global magnetic fluxes and helicity. A Lagrangian variational principle is presented that leads to a new, fully dynamical, relaxed magnetohydrodynamics (RxMHD), such that all static solutions are Taylor states but also allows state with flow. By postulating that some long-lived macroscopic current sheets can act as barriers to relaxation, separating the plasma into multiple relaxation regions, a further generalization, multi-region relaxed magnetohydrodynamics (MRxMHD) is developed.

  19. Plasma relaxation of cold electrons and hot ions

    International Nuclear Information System (INIS)

    Potapenko, I.F.; Sakanaka, P.H.

    1996-01-01

    The relaxation process of a space uniform plasma composed of cold electrons and one species of hot ions studied numerically. Special attention has been paid to the deviation of relaxation from the classical picture which is characterized by a weakly non-isothermic situation. (author). 6 refs., 2 figs

  20. Dynamics of relaxed inflation

    Science.gov (United States)

    Tangarife, Walter; Tobioka, Kohsaku; Ubaldi, Lorenzo; Volansky, Tomer

    2018-02-01

    The cosmological relaxation of the electroweak scale has been proposed as a mechanism to address the hierarchy problem of the Standard Model. A field, the relaxion, rolls down its potential and, in doing so, scans the squared mass parameter of the Higgs, relaxing it to a parametrically small value. In this work, we promote the relaxion to an inflaton. We couple it to Abelian gauge bosons, thereby introducing the necessary dissipation mechanism which slows down the field in the last stages. We describe a novel reheating mechanism, which relies on the gauge-boson production leading to strong electro-magnetic fields, and proceeds via the vacuum production of electron-positron pairs through the Schwinger effect. We refer to this mechanism as Schwinger reheating. We discuss the cosmological dynamics of the model and the phenomenological constraints from CMB and other experiments. We find that a cutoff close to the Planck scale may be achieved. In its minimal form, the model does not generate sufficient curvature perturbations and additional ingredients, such as a curvaton field, are needed.

  1. 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).

  2. 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...

  3. 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.

  4. 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.

  5. 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

  6. The ultrasonic relaxation spectra for furfural molecules undergoing conformational changes

    International Nuclear Information System (INIS)

    Mirzaev, S. Z.; Telyaev, S. Q.; Egamberdiev, K.

    2011-01-01

    The acoustic spectra of liquid furfural have been investigated in the frequency range from 0.1MHz to 150 MHz and at the temperatures from 303.15 K to 333.15 K. The ultrasonic spectra of pure furfural show two relaxation processes. One relaxation process is located in the frequency range ∼0.2 MHz, and the second in the frequency range ∼2 MHz. The process with the lower relaxation frequency has been assigned to the 'X0-cis and X0-trans' internal rotation of furfural molecules. (authors)

  7. Orientation dependence in collision induced electronic relaxation studied through van der Waals complexes with isomeric structures. Invited feature article

    International Nuclear Information System (INIS)

    Cheng, P.Y.; Lapierre, L.; Ju, S.S.; DeRose, P.; Dai, H.L.

    1994-01-01

    Weakly bound molecular complexes with more than one well-defined structures provide us with an unique opportunity to investigate dynamic processes induced by intermolecular interactions with specific orientations. The relative orientation of the two interacting molecules or atoms is defined by the complex structure. The effect of the orientation in the spin changing collisions glyoxal (S 1 ) + Ar → glyoxal (T 1 ) + Ar and acetylene (S 1 ) + Ar → acetylene (T) + Ar have been studied by measuring the intersystem crossing (ISC) rates of the glyoxal(S 1 ).Ar and acetylene(S 1 ).Ar complexes with different isomeric structures. Results show that there is a strong orientation dependence in the ISC of glyoxal(S 1 ) induced by interaction with the Ar atom: the Ar atom positioned in the molecular plane is much more effective than in the out-of-plane position in inducing the S 1 → T 1 transition of glyoxal. On the other hand, studies of acetylene(S 1 ).Ar complexes indicate that the Ar-induced ISC rates are nearly identical for the in-plane and out-of-plane positions. Orientation dependence in the collision induced vibrational relaxation process C 2 H 2 (S 1 , v i ) + Ar → C 2 H 2 (S 1 , v f i ) + Ar is also studied by measuring the vibrational predissociation rates of the acetylene(S 1 ).Ar complex isomers. The results indicate that collisions of C 2 H 2 (S 1 , v 3 = 3, 4) with Ar at two orthogonal orientations are equally effective in causing vibrational relaxation of C 2 H 2 . (orig.)

  8. 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

  9. 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

  10. 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

  11. 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.

  12. Electron spin-lattice relaxation in fractals

    International Nuclear Information System (INIS)

    Shrivastava, K.N.

    1986-08-01

    We have developed the theory of the spin-fracton interaction for paramagnetic ions in fractal structures. The interaction is exponentially damped by the self-similarity length of the fractal and by the range dimensionality d Φ . The relaxation time of the spin due to the absorption and emission of the fracton has been calculated for a general dimensionality called the Raman dimensionality d R , which for the fractons differs from the Hausdorff (fractal) dimensionality, D, as well as from the Euclidean dimensionality, d. The exponent of the energy level separation in the relaxation rate varies with d R d Φ /D. We have calculated the spin relaxation rate due to a new type of Raman process in which one fracton is absorbed to affect a spin transition from one electronic level to another and later another fracton is emitted along with a spin transition such that the difference in the energies of the two fractons is equal to the electronic energy level separation. The temperature and the dimensionality dependence of such a process has been found in several approximations. In one of the approximations where the van Vleck relaxation rate for a spin in a crystal is known to vary with temperature as T 9 , our calculated variation for fractals turns out to be T 6.6 , whereas the experimental value for Fe 3+ in frozen solutions of myoglobin azide is T 6.3 . Since we used d R =4/3 and the fracton range dimensionality d Φ =D/1.8, we expect to measure the dimensionalities of the problem by measuring the temperature dependence of the relaxation times. We have also calculated the shift of the paramagnetic resonance transition for a spin in a fractal for general dimensionalities. (author)

  13. Dynamical relaxation in 2HDM models

    Science.gov (United States)

    Lalak, Zygmunt; Markiewicz, Adam

    2018-03-01

    Dynamical relaxation provides an interesting solution to the hierarchy problem in face of the missing signatures of any new physics in recent experiments. Through a dynamical process taking place in the inflationary phase of the Universe it manages to achieve a small electroweak scale without introducing new states observable in current experiments. Appropriate approximation makes it possible to derive an explicit formula for the final vevs in the double-scanning scenario extended to a model with two Higgs doublets (2HDM). Analysis of the relaxation in the 2HDM confirms that in a general case it is impossible to keep vevs of both scalars small, unless fine-tuning is present or additional symmetries are cast upon the Lagrangian. Within the slightly constrained variant of the 2HDM, where odd powers of the fields’ expectation values are not present (which can be easily enforced by requiring that the doublets have different gauge transformations or by imposing a global symmetry) it is shown that the difference between the vevs of two scalars tends to be proportional to the cutoff. The analysis of the relaxation in 2HDM indicates that in a general case the relaxation would be stopped by the first doublet that gains a vev, with the other one remaining vevless with a mass of the order of the cutoff. This happens to conform with the inert doublet model.

  14. Mechanism of nuclear cross-relaxation in magnetically ordered media

    Energy Technology Data Exchange (ETDEWEB)

    Buishvili, L L; Volzhan, E B; Giorgadze, N P [AN Gruzinskoj SSR, Tbilisi. Inst. Fiziki

    1975-09-01

    A mechanism of two-step nuclear relaxation in magnetic ordered dielectrics is proposed. The case is considered where the energy conservation in the cross relaxation (CR) process is ensured by the lattice itself without spin-spin interactions. Expressions have been obtained describing the temperature dependence of the CR rate. For a nonuniform broadened NMR line it has been shown that the spin-lattice relaxation time for a spin packet taken out from the equilibrium may be determined by the CR time owing to the mechanism suggested. When the quantization axes for electron and nuclear spins coincide, the spin-lattice relaxation is due to the three-magnon mechanism. The cross-relaxation stage has been shown to play a significant role in the range of low temperatures (T<10 deg K) and to become negligible with a temperature increase.

  15. Stress relaxation and hillock growth in thin films

    International Nuclear Information System (INIS)

    Jackson, M.S.; Li, C.Y.

    1978-01-01

    The relaxation of thermal stress in a thin film adhering to a substrate of differing expansion coefficient is discussed. Good agreement is found between literature data on relaxation during isothermal anneals of Pb films at up to 350 0 K and model calculations based on a state variable description of plastic flow. The stress system during relaxation is explored, and the absence of diffusional creep is explained. The plasticity-dominated relaxation process suggested by this analysis is shown to be in good qualitative agreement with data on rapid relaxation over the course of a cycle between room and cryogenic temperatures. The implications of this for long-range material transport in the film are discussed. It is shown that hillock volume should increase over the course of a temperature cycle. Finally, a mechanism for hillock nucleation based on grain boundary sliding is suggested

  16. 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

  17. 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

  18. Axisymmetric force-free states and relaxation of a spheroidal spheromak

    International Nuclear Information System (INIS)

    Throumoulopoulos, G.N.; Pantis, G.

    1990-01-01

    Axisymmetric force-free equilibrium eigenstates for a prolate as well as an oblate spheroidal Spheromak with arbitrary elongation are obtained. In the framework of the Woltjer-Taylor relaxation theory the relaxed states are also identified. A simple hypothesis for the relaxation process is introduced, which implies that the plasma relaxes from multitoroidal formations to a singly toroidal configuration, in qualitative agreement with experimental results. (author)

  19. Axisymmetric force-free states and relaxation of a spheroidal spheromak

    International Nuclear Information System (INIS)

    Throumoulopoulos, G.N.; Pantis, G.

    1990-01-01

    Axisymmetric force-free equilibrium eigenstates for a prolate as well as an oblate spheroidal spheromak with arbitrary elongation are obtained. In the framework of the Woltjer-Taylor relaxation theory the relaxed states are also identified. A simple hypothesis for the relaxation process is introduced which implies that the plasma relaxes from multitoroidal formations to a singly toroidal configuration in qualitative agreement with experimental results. (Author)

  20. Modern problems of relaxation gas dynamics

    International Nuclear Information System (INIS)

    Losev, S.A.; Osipov, A.I.

    1985-01-01

    Some of the dynamical characteristics of relaxation processes are studied. Unfortunately, many dynamical characteristics of relaxation processes, necessary for the solution of important scientific and applied problems, are not known. These problems require further development of experimental methods of the study of nonequilibrium gas. It is known, that gas systems are shifted from the equilibrium by different methods: by acoustic and shock wav es, by means of gas expansion in nozzles and jets, by powerful radiations (laser, first of all), by electric discharges, in burning and combustion devices, etc. Non-equilibrium gas is produced in installations of continuum, impulse and periodic regime. Molecular beams, shock tubes (especially with nozzles), flow and jet installations, aerodynamical tubes, plasmatrons, vessels with a gas, influenced by the strong radiation, burners and combustion devices, where the study of non-euilibrium gas is helpful to solve the problems of the determination of kinetic equations and constants of physico-chemical kinetics

  1. Relaxed states with plasma flow

    International Nuclear Information System (INIS)

    Avinash, K.; Taylor, J.B.

    1991-01-01

    In the theory of relaxation, a turbulent plasma reaches a state of minimum energy subject to constant magnetic helicity. In this state the plasma velocity is zero. Attempts have been made by introducing a number of different constraints, to obtain relaxed states with plasma flow. It is shown that these alternative constraints depend on two self-helicities, one for ions, and one for electrons. However, whereas there are strong arguments for the effective invariance of the original magnetic-helicity, these arguments do not apply to the self-helicities. Consequently the existence of relaxed states with flow remains in doubt. (author)

  2. 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

  3. 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.

  4. State resolved vibrational relaxation modeling for strongly nonequilibrium flows

    Science.gov (United States)

    Boyd, Iain D.; Josyula, Eswar

    2011-05-01

    Vibrational relaxation is an important physical process in hypersonic flows. Activation of the vibrational mode affects the fundamental thermodynamic properties and finite rate relaxation can reduce the degree of dissociation of a gas. Low fidelity models of vibrational activation employ a relaxation time to capture the process at a macroscopic level. High fidelity, state-resolved models have been developed for use in continuum gas dynamics simulations based on computational fluid dynamics (CFD). By comparison, such models are not as common for use with the direct simulation Monte Carlo (DSMC) method. In this study, a high fidelity, state-resolved vibrational relaxation model is developed for the DSMC technique. The model is based on the forced harmonic oscillator approach in which multi-quantum transitions may become dominant at high temperature. Results obtained for integrated rate coefficients from the DSMC model are consistent with the corresponding CFD model. Comparison of relaxation results obtained with the high-fidelity DSMC model shows significantly less excitation of upper vibrational levels in comparison to the standard, lower fidelity DSMC vibrational relaxation model. Application of the new DSMC model to a Mach 7 normal shock wave in carbon monoxide provides better agreement with experimental measurements than the standard DSMC relaxation model.

  5. Relaxed states of tokamak plasmas

    International Nuclear Information System (INIS)

    Kucinski, M.Y.; Okano, V.

    1993-01-01

    The relaxed states of tokamak plasmas are studied. It is assumed that the plasma relaxes to a quasi-steady state which is characterized by a minimum entropy production rate, compatible with a number of prescribed conditions and pressure balance. A poloidal current arises naturally due to the anisotropic resistivity. The minimum entropy production theory is applied, assuming the pressure equilibrium as fundamental constraint on the final state. (L.C.J.A.)

  6. Negative magnetic relaxation in superconductors

    Directory of Open Access Journals (Sweden)

    Krasnoperov E.P.

    2013-01-01

    Full Text Available It was observed that the trapped magnetic moment of HTS tablets or annuli increases in time (negative relaxation if they are not completely magnetized by a pulsed magnetic field. It is shown, in the framework of the Bean critical-state model, that the radial temperature gradient appearing in tablets or annuli during a pulsed field magnetization can explain the negative magnetic relaxation in the superconductor.

  7. Relaxation effects in ferrous complexes

    International Nuclear Information System (INIS)

    Nicolini, C.; Mathieu, J.P.; Chappert, J.

    1976-01-01

    The slow relaxation mechanism of the Fe 2+ ion in the tri-fluorinated TF(acac) and hexafluorinated HF(acac) complexes of Fe(II) acetylacetonate was investigated. The 300K and 77K Moessbauer spectra for TF(acac) consist in a slightly asymmetric quadrupole doublet. On the contrary, at 4.2K the higher energy line is strongly widened; that is typical of a slowing down in the electron relaxation frequency [fr

  8. F{sup 19} relaxation in non-magnetic hexafluorides; Contribution a l'etude de la relaxation des fluors dans les hexafluorures non magnetiques

    Energy Technology Data Exchange (ETDEWEB)

    Rigny, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-12-01

    The interesting properties of the fluorine magnetic resonance in the hexafluorides of molybdenum, tungsten and uranium, are very much due to large anisotropies of the chemical shift tensors. In the solid phases these anisotropies, the values of which are deduced from line shape studies, allow one to show that the molecules undergo hindered rotations about the metal atom. The temperature and frequency dependence of the fluorine longitudinal relaxation times shows that the relaxation is due to the molecular motion. The dynamical parameters of this motion are then deduced from the complete study of the fluorine relaxation in the rotating frame. In the liquid phases, the existence of anisotropies allows an estimation of the different contributions to the relaxation. In particular, the frequency and temperature dependence of the relaxation shows it to be dominated by the spin-rotation interaction. We have shown that the strength of this interaction can be deduced from the chemical shifts, and the angle through which the molecule rotates quasi-freely can be determined. In the hexafluorides, this angle is roughly one radian at 70 C, and with the help of this value, the friction coefficients which describe the intermolecular interactions are discussed. (author) [French] Les proprietes de la resonance magnetique des fluors dans les hexafluorures de molybdene, tungstene et uranium sont influencees par l'existence de deplacements chimiques tres anisotropes. Dans les phases solides, la valeur de cette anisotropie peut etre determinee par l'analyse des formes de raies et son existence permet de montrer que les molecules sont en rotation empechee autour de leur atome central. L'etude du temps de relaxation longitudinal en fonction de la temperature et de la frequence montre que la relaxation est due aux mouvements moleculaires, aux plus hautes temperatures. Les proprietes dynamiques du mouvement sont obtenues par l'etude complete de la relaxation spin-reseau dans le referentiel

  9. Non-monotonic behaviour in relaxation dynamics of image restoration

    International Nuclear Information System (INIS)

    Ozeki, Tomoko; Okada, Masato

    2003-01-01

    We have investigated the relaxation dynamics of image restoration through a Bayesian approach. The relaxation dynamics is much faster at zero temperature than at the Nishimori temperature where the pixel-wise error rate is minimized in equilibrium. At low temperature, we observed non-monotonic development of the overlap. We suggest that the optimal performance is realized through premature termination in the relaxation processes in the case of the infinite-range model. We also performed Markov chain Monte Carlo simulations to clarify the underlying mechanism of non-trivial behaviour at low temperature by checking the local field distributions of each pixel

  10. Dissipation and the relaxation to equilibrium

    International Nuclear Information System (INIS)

    Evans, Denis J; Williams, Stephen R; Searles, Debra J

    2009-01-01

    Using the recently derived dissipation theorem and a corollary of the transient fluctuation theorem (TFT), namely the second-law inequality, we derive the unique time independent, equilibrium phase space distribution function for an ergodic Hamiltonian system in contact with a remote heat bath. We prove under very general conditions that any deviation from this equilibrium distribution breaks the time independence of the distribution. Provided temporal correlations decay, we show that any nonequilibrium distribution that is an even function of the momenta eventually relaxes (not necessarily monotonically) to the equilibrium distribution. Finally we prove that the negative logarithm of the microscopic partition function is equal to the thermodynamic Helmholtz free energy divided by the thermodynamic temperature and Boltzmann's constant. Our results complement and extend the findings of modern ergodic theory and show the importance of dissipation in the process of relaxation towards equilibrium

  11. Effective temperature in relaxation of Coulomb glasses.

    Science.gov (United States)

    Somoza, A M; Ortuño, M; Caravaca, M; Pollak, M

    2008-08-01

    We study relaxation in two-dimensional Coulomb glasses up to macroscopic times. We use a kinetic Monte Carlo algorithm especially designed to escape efficiently from deep valleys around metastable states. We find that, during the relaxation process, the site occupancy follows a Fermi-Dirac distribution with an effective temperature much higher than the real temperature T. Long electron-hole excitations are characterized by T(eff), while short ones are thermalized at T. We argue that the density of states at the Fermi level is proportional to T(eff) and is a good thermometer to measure it. T(eff) decreases extremely slowly, roughly as the inverse of the logarithm of time, and it should affect hopping conductance in many experimental circumstances.

  12. Nuclear magnetic relaxation by the dipolar EMOR mechanism: General theory with applications to two-spin systems.

    Science.gov (United States)

    Chang, Zhiwei; Halle, Bertil

    2016-02-28

    In aqueous systems with immobilized macromolecules, including biological tissue, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. We have embarked on a systematic program to develop, from the stochastic Liouville equation, a general and rigorous theory that can describe relaxation by the dipolar EMOR mechanism over the full range of exchange rates, dipole coupling strengths, and Larmor frequencies. Here, we present a general theoretical framework applicable to spin systems of arbitrary size with symmetric or asymmetric exchange. So far, the dipolar EMOR theory is only available for a two-spin system with symmetric exchange. Asymmetric exchange, when the spin system is fragmented by the exchange, introduces new and unexpected phenomena. Notably, the anisotropic dipole couplings of non-exchanging spins break the axial symmetry in spin Liouville space, thereby opening up new relaxation channels in the locally anisotropic sites, including longitudinal-transverse cross relaxation. Such cross-mode relaxation operates only at low fields; at higher fields it becomes nonsecular, leading to an unusual inverted relaxation dispersion that splits the extreme-narrowing regime into two sub-regimes. The general dipolar EMOR theory is illustrated here by a detailed analysis of the asymmetric two-spin case, for which we present relaxation dispersion profiles over a wide range of conditions as well as analytical results for integral relaxation rates and time-dependent spin modes in the zero-field and motional-narrowing regimes. The general theoretical framework presented here will enable a quantitative analysis of frequency-dependent water-proton longitudinal relaxation in model systems with immobilized macromolecules and, ultimately, will provide a rigorous link between relaxation-based magnetic resonance image contrast and molecular parameters.

  13. On the relaxation of cold electrons and hot ions

    International Nuclear Information System (INIS)

    Potapenko, I.F.; Bobylev, A.V.; Azevedo, C.A. de; Sakanaka, P.H.; Assis, A.S. de

    1998-01-01

    The relaxation process of a space uniform plasma composed of cold electrons and one species of hot ions is studied numerically using one- and two-dimensional Landau - Fokker - Planck codes. Relaxation of a monoenergetic ion beam is considered in possibly extreme temperature regimes. Special attention is paid to the deviation of the relaxation process from the classical picture, which is characterized by the close initial temperatures T e >(m e /m i ) 1/3 T i . The present results give quite a clear idea of the relaxation picture for any initial temperatures also in extreme temperature regimes. A difference scheme, preserving the number of particles and the energy, gives the possibility of solving the problem numerically without error accumulation, except for machine errors. copyright 1998 American Institute of Physics

  14. Batch Covariance Relaxation (BCR) Adaptive Processing.

    Science.gov (United States)

    1981-08-01

    leads to the equivalent bandpass transfer function K Pk-8) Bpp (s) =17 - 22 where C2I is the radian IF frequency normalized by wc. Assuming, tacitly...transfer function in (2-3) is given by H +(f + fE) = H+ Bpp (I + 6 ) (2-13) provided that f and f, are understood to be normalized by fc = wc/2r. In...4..J - tj, 45I2 a I a N 1A CZ~ IJ~oa 1,1 2.0 X : Z 1-3 1 a * N -- e - -o 0 (A -1- 1U z 0 8 Or I W *IA O! IU fau a :at oc- -MZ a Iaaa a a m :wU I..- 1

  15. Pulse Detonation Physiochemical and Exhaust Relaxation Processes

    Science.gov (United States)

    2006-05-01

    based on total time to detonation and detonation percentage. Nomenclature A = Arrehenius Constant Ea = Activation Energy Ecrit = Critical...the precision uncertainties vary for each data point. Therefore, the total experimental uncertainty will vary by data point. A comprehensive bias

  16. 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.

  17. 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 ...

  18. Raman Spectra and Intermolecular Hydrogen Bonds of Quinoline in Solutions

    International Nuclear Information System (INIS)

    Tukhvatullin, F.H.; Jumabayev, A.; Hushvaktov, H.; Absanov, A.; Hudoyberdiev, B.

    2012-01-01

    The half-widths of the 1014- and 1033-cm -1 bands of the Raman spectrum of quinoline at its dilution in neutral solvents (benzene, CCl 4 ) are narrowed by 1.3-1.5 times at high dilutions. This effect is associated with the increased time of the vibrational relaxation. For the 520-cm -1 band in pure liquid quinoline, the parallel polarized component at 20 o C is asymmetric in the high-frequency region. The shape of the perpendicular polarized component is complicated. A non-coincidence of the peak frequencies of the parallel and perpendicular polarized components is observed (∼ 2 cm -1 ). Quantum-chemical calculations showed that, in the region of 520 cm -1 for a monomer molecule, we should really have two near located lines with the wavenumbers 530 and 527 cm -1 (scaling factor 0.97), and with the depolarization ratios 0.61 and 0.26. In the solutions with propan-2-ol, the 1033.8-cm -1 band becomes of a doublet character. The resolution of the doublet becomes better by the dilution of a binary quinoline-alcohol solution with a large amount of a neutral solvent (benzene). The wavenumbers of bands in the triple mixture are 1033 cm -1 and 1039 cm -1 . The doublet nature of the band in the binary and triple mixtures is associated with the presence of monomer molecules and quinoline-propan-2-ol aggregates (the high-frequency line) in the liquid mixture. Quantum-chemical calculations showed that the hydrogen bonds with a length of 1.958 A and an energy gain of 22.0 kJ/mole can be formed between molecules of quinoline and alcohol. The formation of aggregates can be also detected in the 820-cm -1 band of propan-2-ol. A similar picture is observed for the 667-cm -1 band of chloroform in its solution with quinoline.

  19. Biexciton relaxation associated with dissociation into a surface polariton pair in semiconductor films

    Science.gov (United States)

    Mitsumori, Yasuyoshi; Matsuura, Shimpei; Uchiyama, Shoichi; Saito, Kentarao; Edamatsu, Keiichi; Nakayama, Masaaki; Ajiki, Hiroshi

    2018-04-01

    We study the biexciton relaxation process in CuCl films ranging from 6 to 200 nm. The relaxation time is measured as the dephasing time and the lifetime. We observe a unique thickness dependence of the biexciton relaxation time and also obtain an ultrafast relaxation time with a timescale as short as 100 fs, while the exciton lifetime monotonically decreases with increasing thickness. By analyzing the exciton-photon coupling energy for a surface polariton, we theoretically calculate the biexciton relaxation time as a function of the thickness. The calculated dependence qualitatively reproduces the observed relaxation time, indicating that the biexciton dissociation into a surface polariton pair is one of the major biexciton relaxation processes.

  20. 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

  1. Relaxation and kinetics in scalar field theories

    International Nuclear Information System (INIS)

    Boyanovsky, D.; Lawrie, I.D.; Lee, D.

    1996-01-01

    A new approach to the dynamics of relaxation and kinetics of thermalization in a scalar field theory is presented that incorporates the relevant time scales through the resummation of hard thermal loops. An alternative derivation of the kinetic equations for the open-quote open-quote quasiparticle close-quote close-quote distribution functions is obtained that allows a clear understanding of the different open-quote open-quote coarse-graining close-quote close-quote approximations usually involved in a kinetic description. This method leads to a systematic perturbative expansion to obtain the kinetic equations including hard thermal loop resummation and to an improvement including renormalization, off-shell effects, and contributions that change chemical equilibrium on short time scales. As a by-product of these methods we establish the equivalence between the relaxation time scale in the linearized equation of motion of the quasiparticles and the thermalization time scale of the quasiparticle distribution function in the open-quote open-quote relaxation time approximation close-quote close-quote including hard thermal loop effects. Hard thermal loop resummation dramatically modifies the scattering rate for long wavelength modes as compared to the usual (semi)classical estimate. Relaxation and kinetics are studied both in the unbroken and broken symmetry phases of the theory. The broken symmetry phase also provides the setting to obtain the contribution to the kinetic equations from processes that involve decay of a heavy scalar into light scalar particles in the medium. copyright 1996 The American Physical Society

  2. Peeling mode relaxation ELM model

    International Nuclear Information System (INIS)

    Gimblett, C. G.

    2006-01-01

    This paper discusses an approach to modelling Edge Localised Modes (ELMs) in which toroidal peeling modes are envisaged to initiate a constrained relaxation of the tokamak outer region plasma. Relaxation produces both a flattened edge current profile (which tends to further destabilise a peeling mode), and a plasma-vacuum negative current sheet which has a counteracting stabilising influence; the balance that is struck between these two effects determines the radial extent (rE) of the ELM relaxed region. The model is sensitive to the precise position of the mode rational surfaces to the plasma surface and hence there is a 'deterministic scatter' in the results that has an accord with experimental data. The toroidal peeling stability criterion involves the edge pressure, and using this in conjunction with predictions of rE allows us to evaluate the ELM energy losses and compare with experiment. Predictions of trends with the edge safety factor and collisionality are also made

  3. Relaxation-phenomena in LiAl/FeS-cells

    Science.gov (United States)

    Borger, W.; Kappus, W.; Panesar, H. S.

    A theoretical model of the capacity of strongly relaxing electrochemical systems is applied to the LiAl/FeS system. Relaxation phenomena in LiAl and FeS electrodes can be described by this model. Experimental relaxation data indicate that lithium transport through the alpha-LiAl layer to the particle surface is the capacity limiting process at high discharge current density in the LiAl electrode in LiCl-KCl and LiF-LiCl-LiBr mixtures. Strong relaxation is observed in the FeS electrode with LiCl-KCl electrolyte caused by lithium concentration gradients and precipitation of KCl in the pores.

  4. Dielectric relaxation studies of dilute solutions of amides

    Energy Technology Data Exchange (ETDEWEB)

    Malathi, M.; Sabesan, R.; Krishnan, S

    2003-11-15

    The dielectric constants and dielectric losses of formamide, acetamide, N-methyl acetamide, acetanilide and N,N-dimethyl acetamide in dilute solutions of 1,4-dioxan/benzene have been measured at 308 K using 9.37 GHz, dielectric relaxation set up. The relaxation time for the over all rotation {tau}{sub (1)} and that for the group rotation {tau}{sub (2)} of (the molecules were determined using Higasi's method. The activation energies for the processes of dielectric relaxation and viscous flow were determined by using Eyring's rate theory. From relaxation time behaviour of amides in non-polar solvent, solute-solvent and solute-solute type of molecular association is proposed.

  5. Topology Synthesis of Structures Using Parameter Relaxation and Geometric Refinement

    Science.gov (United States)

    Hull, P. V.; Tinker, M. L.

    2007-01-01

    Typically, structural topology optimization problems undergo relaxation of certain design parameters to allow the existence of intermediate variable optimum topologies. Relaxation permits the use of a variety of gradient-based search techniques and has been shown to guarantee the existence of optimal solutions and eliminate mesh dependencies. This Technical Publication (TP) will demonstrate the application of relaxation to a control point discretization of the design workspace for the structural topology optimization process. The control point parameterization with subdivision has been offered as an alternative to the traditional method of discretized finite element design domain. The principle of relaxation demonstrates the increased utility of the control point parameterization. One of the significant results of the relaxation process offered in this TP is that direct manufacturability of the optimized design will be maintained without the need for designer intervention or translation. In addition, it will be shown that relaxation of certain parameters may extend the range of problems that can be addressed; e.g., in permitting limited out-of-plane motion to be included in a path generation problem.

  6. A simple measurement method of molecular relaxation in a gas by reconstructing acoustic velocity dispersion

    Science.gov (United States)

    Zhu, Ming; Liu, Tingting; Zhang, Xiangqun; Li, Caiyun

    2018-01-01

    Recently, a decomposition method of acoustic relaxation absorption spectra was used to capture the entire molecular multimode relaxation process of gas. In this method, the acoustic attenuation and phase velocity were measured jointly based on the relaxation absorption spectra. However, fast and accurate measurements of the acoustic attenuation remain challenging. In this paper, we present a method of capturing the molecular relaxation process by only measuring acoustic velocity, without the necessity of obtaining acoustic absorption. The method is based on the fact that the frequency-dependent velocity dispersion of a multi-relaxation process in a gas is the serial connection of the dispersions of interior single-relaxation processes. Thus, one can capture the relaxation times and relaxation strengths of N decomposed single-relaxation dispersions to reconstruct the entire multi-relaxation dispersion using the measurements of acoustic velocity at 2N  +  1 frequencies. The reconstructed dispersion spectra are in good agreement with experimental data for various gases and mixtures. The simulations also demonstrate the robustness of our reconstructive method.

  7. Composition effect of potassium-borate glasses on their relaxation properties

    International Nuclear Information System (INIS)

    Lomovskoj, V.A.; Bartenev, G.M.

    1995-01-01

    Relaxation processes in potassium-borate glasses have been investigated in detail for the first time. It is shown that low-temperature β-process of relaxation relating to rotational mobility of the B-O bond is the same for all potassium-borate glasses and B 2 O 3 . The process of β k -relaxation related to diffusion mobility of potassium ions depends on the composition of the glasses in the same way as α-relaxation (glass formation).12 refs., 10 figs., 2 tabs

  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. 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

  10. 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

  11. 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…

  12. 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…

  13. 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.

  14. Parameterization of NMR relaxation curves in terms of logarithmic moments of the relaxation time distribution.

    Science.gov (United States)

    Petrov, Oleg V; Stapf, Siegfried

    2017-06-01

    This work addresses the problem of a compact and easily comparable representation of multi-exponential relaxation data. It is often convenient to describe such data in a few parameters, all being of physical significance and easy to interpret, and in such a way that enables a model-free comparison between different groups of samples. Logarithmic moments (LMs) of the relaxation time constitute a set of parameters which are related to the characteristic relaxation time on the log-scale, the width and the asymmetry of an underlying distribution of exponentials. On the other hand, the calculation of LMs does not require knowing the actual distribution function and is reduced to a numerical integration of original data. The performance of this method has been tested on both synthetic and experimental NMR relaxation data which differ in a signal-to-noise ratio, the sampling range and the sampling rate. The calculation of two lower-order LMs, the log-mean time and the log-variance, has proved robust against deficiencies of the experiment such as scattered data point and incomplete sampling. One may consider using them as such to monitor formation of a heterogeneous structure, e.g., in phase separation, vitrification, polymerization, hydration, aging, contrast agent propagation processes. It may also assist in interpreting frequency and temperature dependences of relaxation, revealing a crossover from slow to fast exchange between populations. The third LM was found to be a less reliable quantity due to its susceptibility to the noise and must be used with caution. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Parameterization of NMR relaxation curves in terms of logarithmic moments of the relaxation time distribution

    Science.gov (United States)

    Petrov, Oleg V.; Stapf, Siegfried

    2017-06-01

    This work addresses the problem of a compact and easily comparable representation of multi-exponential relaxation data. It is often convenient to describe such data in a few parameters, all being of physical significance and easy to interpret, and in such a way that enables a model-free comparison between different groups of samples. Logarithmic moments (LMs) of the relaxation time constitute a set of parameters which are related to the characteristic relaxation time on the log-scale, the width and the asymmetry of an underlying distribution of exponentials. On the other hand, the calculation of LMs does not require knowing the actual distribution function and is reduced to a numerical integration of original data. The performance of this method has been tested on both synthetic and experimental NMR relaxation data which differ in a signal-to-noise ratio, the sampling range and the sampling rate. The calculation of two lower-order LMs, the log-mean time and the log-variance, has proved robust against deficiencies of the experiment such as scattered data point and incomplete sampling. One may consider using them as such to monitor formation of a heterogeneous structure, e.g., in phase separation, vitrification, polymerization, hydration, aging, contrast agent propagation processes. It may also assist in interpreting frequency and temperature dependences of relaxation, revealing a crossover from slow to fast exchange between populations. The third LM was found to be a less reliable quantity due to its susceptibility to the noise and must be used with caution.

  16. The effects of bone on proton NMR relaxation times of surrounding liquids

    Science.gov (United States)

    Davis, C. A.; Genant, H. K.; Dunham, J. S.

    1986-01-01

    Preliminary attempts by our group at UCSF to assess fat content of vertebral marrow in the lumbar spine using relaxation time information demonstrated that the presence of trabecular bone affects relaxation times. The objective of this work was a thorough study of the effects of bone on NMR relaxation characteristics of surrounding liquids. Trabecular bone from autopsy specimens was ground up and sifted into a series of powders with graded densities ranging from 0.3 gm/cc to 0.8 gm/cc. Each powder was placed first in n-saline and then in cottonseed oil. With spectroscopy, spin-lattice relaxation times (T1) and effective spin-spin relaxation times (T2*) were measured for each liquid in each bone powder. As bone density and surface to volume ratio increased, T1 decreased faster for saline than for oil. T2* decreased significantly for both water and oil as the surface to volume ratio increased. It was concluded that effects of water on T1 could be explained by a surface interaction at the bone/liquid interface, which restricted rotational and translational motion of nearby molecules. The T1s of oil were not affected since oil molecules are nonpolar, do not participate in significant intermolecular hydrogen bonding, and therefore would not be expected to interact strongly with the bone surface. Effects on T2* could be explained by local magnetic field inhomogeneities created by discontinuous magnetic susceptibility near the bone surface. These preliminary results suggest that water in contact with trabecular bone in vivo will exhibit shortened relaxation times.

  17. Relaxation properties in classical diamagnetism

    Science.gov (United States)

    Carati, A.; Benfenati, F.; Galgani, L.

    2011-06-01

    It is an old result of Bohr that, according to classical statistical mechanics, at equilibrium a system of electrons in a static magnetic field presents no magnetization. Thus a magnetization can occur only in an out of equilibrium state, such as that produced through the Foucault currents when a magnetic field is switched on. It was suggested by Bohr that, after the establishment of such a nonequilibrium state, the system of electrons would quickly relax back to equilibrium. In the present paper, we study numerically the relaxation to equilibrium in a modified Bohr model, which is mathematically equivalent to a billiard with obstacles, immersed in a magnetic field that is adiabatically switched on. We show that it is not guaranteed that equilibrium is attained within the typical time scales of microscopic dynamics. Depending on the values of the parameters, one has a relaxation either to equilibrium or to a diamagnetic (presumably metastable) state. The analogy with the relaxation properties in the Fermi Pasta Ulam problem is also pointed out.

  18. Onsager relaxation of toroidal plasmas

    International Nuclear Information System (INIS)

    Samain, A.; Nguyen, F.

    1997-01-01

    The slow relaxation of isolated toroidal plasmas towards their thermodynamical equilibrium is studied in an Onsager framework based on the entropy metric. The basic tool is a variational principle, equivalent to the kinetic equation, involving the profiles of density, temperature, electric potential, electric current. New minimization procedures are proposed to obtain entropy and entropy production rate functionals. (author)

  19. Anisotropic spin relaxation in graphene

    NARCIS (Netherlands)

    Tombros, N.; Tanabe, S.; Veligura, A.; Jozsa, C.; Popinciuc, M.; Jonkman, H. T.; van Wees, B. J.

    2008-01-01

    Spin relaxation in graphene is investigated in electrical graphene spin valve devices in the nonlocal geometry. Ferromagnetic electrodes with in-plane magnetizations inject spins parallel to the graphene layer. They are subject to Hanle spin precession under a magnetic field B applied perpendicular

  20. Stochastic and Chaotic Relaxation Oscillations

    NARCIS (Netherlands)

    Grasman, J.; Roerdink, J.B.T.M.

    1988-01-01

    For relaxation oscillators stochastic and chaotic dynamics are investigated. The effect of random perturbations upon the period is computed. For an extended system with additional state variables chaotic behavior can be expected. As an example, the Van der Pol oscillator is changed into a

  1. Tensions relaxation in Zircaloy-4

    International Nuclear Information System (INIS)

    Cuniberti, A.M.; Picasso, A.C.

    1990-01-01

    Traction and stress relaxation studies were performed on polycrystalline Zry-4 at room temperature. The effect of loading velocity on the plastic behaviour of the material is discussed, analysing log σ vs. log dε/dt at different deformation levels. The contribution introduced by the testing machine was taken into account in data evaluation. (Author). 7 refs., 3 figs., 3 tabs

  2. Ultra-fast relaxation kinetics in semiconductors

    International Nuclear Information System (INIS)

    Luzzi, R.

    1983-01-01

    It is presented a brief description of relaxation processes in highly excited semiconductor plasmas (HESP). Comparison with experimental data obtained by means of ultra-fast laser light spectroscopy (UFLS) is made. Some aspects of response funtion theory in systems far-from-equilibrium are reviewed in Section II. In Section III we present some comments on the question of nonequilibrium thermodynamics relevant to the problem to be considered. In last section we present a brief summary of the different aspects of the subject. (author) [pt

  3. Charge imbalance: its relaxation, diffusion and oscillation

    International Nuclear Information System (INIS)

    Pethick, C.J.

    1981-01-01

    In this article, the authors use a model for charge density based on two charge components: the normal quasiparticle component and the superfluid/condensate component. Based on the quasiparticle Boltzmann equation, this two-component model, when used in nonequilibrium contexts, is fruitful in describing a variety of charge-imbalance phenomena in superconductors. The authors discuss various methods of generating charge-imbalances, charge-imbalance relaxation processes (such as phonons, impurity scattering and magnetic impurities) and applications of the two-component model of charge imbalance to spatially inhomogeneous conditions

  4. Ultra-fast relaxation kinetics in semiconductors

    International Nuclear Information System (INIS)

    Luzzi, R.

    1983-01-01

    It is presented a brief description of relaxation processes in highly excited semiconductor plasmas (HESP). Comparison with experimental data obtained by means of ultra-fast laser light spectroscopy (UFLS) is made. Some aspects of response function theory in systems far-from-equilibrium are reviewed in Section II. In Section III some comments on the question of nonequilibrium thermodynamics relevant to the problem to be considered are presented. In last Section a brief summary of the different aspects of the subject is also presented. (Author) [pt

  5. Sleep, Stress & Relaxation: Rejuvenate Body & Mind

    Science.gov (United States)

    Sleep, Stress & Relaxation: Rejuvenate Body & Mind; Relieve Stress; best ways to relieve stress; best way to relieve stress; different ways to relieve stress; does smoking relieve stress; does tobacco relieve stress; how can I relieve stress; how can you relieve stress; how do I relieve stress; reduce stress; does smoking reduce stress; how can I reduce stress; how to reduce stress; reduce stress; reduce stress levels; reducing stress; smoking reduce stress; smoking reduces stress; stress reducing techniques; techniques to reduce stress; stress relief; best stress relief; natural stress relief; need stress relief; relief for stress; relief from stress; relief of stress; smoking and stress relief; smoking for stress relief; smoking stress relief; deal with stress; dealing with stress; dealing with anger; dealing with stress; different ways of dealing with stress; help dealing with stress; how to deal with anger; how to deal with stress; how to deal with stress when quitting smoking; stress management; free stress management; how can you manage stress; how do you manage stress; how to manage stress; manage stress; management of stress; management stress; managing stress; strategies for managing stress; coping with stress; cope with stress; copeing with stress; coping and stress; coping skills for stress; coping strategies for stress; coping strategies with stress; coping strategy for stress; coping with stress; coping with stress and anxiety; emotional health; emotional health; emotional health article; emotional health articles; deep relaxation; deep breathing relaxation techniques; deep muscle relaxation; deep relaxation; deep relaxation meditation; deep relaxation technique; deep relaxation techniques; meditation exercises; mindful exercises; mindful meditation exercises; online relaxation exercises; relaxation breathing exercises; relaxation exercise; relaxation exercises; stress relaxation; methods of relaxation for stress; relax stress; relax techniques stress

  6. Relaxation creep model of impending earthquake

    Energy Technology Data Exchange (ETDEWEB)

    Morgounov, V. A. [Russian Academy of Sciences, Institute of Physics of the Earth, Moscow (Russian Federation)

    2001-04-01

    The alternative view of the current status and perspective of seismic prediction studies is discussed. In the problem of the ascertainment of the uncertainty relation Cognoscibility-Unpredictability of Earthquakes, priorities of works on short-term earthquake prediction are defined due to the advantage that the final stage of nucleation of earthquake is characterized by a substantial activation of the process while its strain rate increases by the orders of magnitude and considerably increased signal-to-noise ratio. Based on the creep phenomenon under stress relaxation conditions, a model is proposed to explain different images of precursors of impending tectonic earthquakes. The onset of tertiary creep appears to correspond to the onset of instability and inevitably fails unless it unloaded. At this stage, the process acquires the self-regulating character to the greatest extent the property of irreversibility, one of the important components of prediction reliability. Data in situ suggest a principal possibility to diagnose the process of preparation by ground measurements of acoustic and electromagnetic emission in the rocks under constant strain in the condition of self-relaxed stress until the moment of fracture are discussed in context. It was obtained that electromagnetic emission precedes but does not accompany the phase of macrocrak development.

  7. Nonequilibrium thermodynamics and information theory: basic concepts and relaxing dynamics

    International Nuclear Information System (INIS)

    Altaner, Bernhard

    2017-01-01

    Thermodynamics is based on the notions of energy and entropy. While energy is the elementary quantity governing physical dynamics, entropy is the fundamental concept in information theory. In this work, starting from first principles, we give a detailed didactic account on the relations between energy and entropy and thus physics and information theory. We show that thermodynamic process inequalities, like the second law, are equivalent to the requirement that an effective description for physical dynamics is strongly relaxing. From the perspective of information theory, strongly relaxing dynamics govern the irreversible convergence of a statistical ensemble towards the maximally non-commital probability distribution that is compatible with thermodynamic equilibrium parameters. In particular, Markov processes that converge to a thermodynamic equilibrium state are strongly relaxing. Our framework generalizes previous results to arbitrary open and driven systems, yielding novel thermodynamic bounds for idealized and real processes. (paper)

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

    Indian Academy of Sciences (India)

    water is used in nuclear reactors and is about to become an important fuel analog for possible control of thermonuclear processes. Various physicochemical proper- .... This results in the fact that in the region of standard thermodynamic temperature, the replacement of hydrogen by deuterium either hardly changes the.

  9. Effect of carrier relaxation lifetime on the performance of InAs/InP quantum-dash lasers

    KAUST Repository

    Khan, Mohammed Zahed Mustafa

    2011-12-01

    The effect of carrier relaxation process into the quantum dash (Qdash) ground state (GS) is examined theoretically by carrier-photon rate equation model incorporating the inhomogeneous broadening. Increase in the relaxation time and the inhomogeneous broadening degrades the threshold current density. Moreover, our results show that a relaxation time of less than 2 ps gives optimum laser performance. © 2011 IEEE.

  10. Tailoring intra- and intermolecular properties : from cyclophanes to daisy chains

    OpenAIRE

    Rotzler, Jürgen Stefan

    2012-01-01

    Todays high-tech society is striving for faster, cheaper and higher performing devices in all circumstances. Traditional materials have long since reached their limits making the search for new materials with altered properties inevitable. Easy processable, long-term stable polymeric materials with improved handling or switchable properties for use in plastics, conducting single molecular wires, switches, rectifiers in computer industry, nonlinear optic materials for data transmission at the ...

  11. Intermolecular interactions of thrombospondins drive their accumulation in extracellular matrix

    OpenAIRE

    Kim, Dae Joong; Christofidou, Elena D.; Keene, Douglas R.; Hassan Milde, Marwah; Adams, Josephine C.

    2015-01-01

    Thrombospondins participate in many aspects of tissue organization in adult tissue homeostasis, and their dysregulation contributes to pathological processes such as fibrosis and tumor progression. The incorporation of thrombospondins into extracellular matrix (ECM) as discrete puncta has been documented in various tissue and cell biological contexts, yet the underlying mechanisms remain poorly understood. We find that collagen fibrils are disorganized in multiple tissues of Thbs1 −/− mice. I...

  12. Differential multiple quantum relaxation caused by chemical exchange outside the fast exchange limit

    International Nuclear Information System (INIS)

    Wang Chunyu; Palmer, Arthur G.

    2002-01-01

    Differential relaxation of multiple quantum coherences is a signature for chemical exchange processes in proteins. Previous analyses of experimental data have used theoretical descriptions applicable only in the limit of fast exchange. Theoretical expressions for differential relaxation rate constants that are accurate outside fast exchange are presented for two-spin-system subject to two-site chemical exchange. The theoretical expressions are validated using experimental results for 15 N- 1 H relaxation in basic pancreatic trypsin inhibitor. The new theoretical expression is valuable for identification and characterization of exchange processes in proteins using differential relaxation of multiple quantum coherences

  13. Dynamic and structural characterisation of micellar solutions of surfactants by spin relaxation and translational diffusion

    International Nuclear Information System (INIS)

    Mahieu, Nathalie

    1992-01-01

    The work reported in this research thesis aimed at characterizing micellar phases formed by some surfactants (sodium carboxylates) in aqueous solution. After some recalls on nuclear magnetic resonance dealing with spin relaxation (longitudinal relaxation, transverse relaxation, relaxation in the rotating coordinate system, and crossed relaxation), and comments on the dipolar mechanism responsible of relaxation phenomena, the author presents the methods used for relaxation parameter measurement and the data processing software issued from experiments. He presents experiments which allowed the self-diffusion coefficient to be measured, reports data processing, and addresses problems of special diffusion and of coherence transfers during diffusion measurements. Results of proton relaxation measurements are then presented and discussed. They are used to determine the micellar state of the studied carboxylates. The case of the oleate is also addressed. Measurements of carbon-13 relaxation times are reported, and exploited in terms of structural parameters by using the Relaxator software. An original method of the hetero-nuclear Overhauser method is presented, and used to assess the average distance between water molecules and micelle surface [fr

  14. Relaxation Techniques to Manage IBS Symptoms

    Science.gov (United States)

    ... for 15–20 seconds and then begin again. Progressive Muscle Relaxation This method of relaxation focuses on ... helpful, please consider supporting IFFGD with a small tax- deductible donation. Make Donation Adapted from IFFGD Publication # ...

  15. Relaxation and Distraction in Experimental Desensitization.

    Science.gov (United States)

    Weir, R. O.; Marshall, W. L.

    1980-01-01

    Compared experimental desensitization with a procedure that replaced relaxation with a distraction task and with an approach that combined both relaxation and distraction. Desensitization generally was more effective than the other two procedures. (Author)

  16. Relaxation as a Factor in Semantic Desensitization

    Science.gov (United States)

    Bechtel, James E.; McNamara, J. Regis

    1975-01-01

    Relaxation and semantic desensitization were used to alleviate the fear of phobic females. Results showed that semantic desensitization, alone or in combination with relaxation, failed to modify the evaluative meanings evoked by the feared object. (SE)

  17. Novel spin dynamics in ferrimagnetic molecular chains from 1H NMR and μSR spin-lattice relaxation measurements

    International Nuclear Information System (INIS)

    Micotti, E.; Lascialfari, A.; Rigamonti, A.; Aldrovandi, S.; Caneschi, A.; Gatteschi, D.; Bogani, L.

    2004-01-01

    The spin dynamics in the helical chain Co(hfac) 2 NITPhOMe has been investigated by 1 H NMR and μSR relaxation. In the temperature range 15< T<60 K, the results are consistent with the relaxation of the homogeneous magnetization. For T≤15 K, NMR and μSR evidence a second spin relaxation mechanism, undetected by the magnetization measurements. From the analysis of these data, insights on this novel relaxation process are derived

  18. Novel spin dynamics in ferrimagnetic molecular chains from 1H NMR and μSR spin-lattice relaxation measurements

    Science.gov (United States)

    Micotti, E.; Lascialfari, A.; Rigamonti, A.; Aldrovandi, S.; Caneschi, A.; Gatteschi, D.; Bogani, L.

    2004-05-01

    The spin dynamics in the helical chain Co(hfac) 2NITPhOMe has been investigated by 1H NMR and μSR relaxation. In the temperature range 15relaxation of the homogeneous magnetization. For T⩽15 K, NMR and μSR evidence a second spin relaxation mechanism, undetected by the magnetization measurements. From the analysis of these data, insights on this novel relaxation process are derived.

  19. Plasmon-mediated energy relaxation in graphene

    Energy Technology Data Exchange (ETDEWEB)

    Ferry, D. K. [School of Electrical, Computer, and Energy Engineering, Arizona State University, Tempe, Arizona 85287-5706 (United States); Somphonsane, R. [Department of Physics, King Mongkut' s Institute of Technology, Ladkrabang, Bangkok 10520 (Thailand); Ramamoorthy, H.; Bird, J. P. [Department of Electrical Engineering, University at Buffalo, the State University of New York, Buffalo, New York 14260-1500 (United States)

    2015-12-28

    Energy relaxation of hot carriers in graphene is studied at low temperatures, where the loss rate may differ significantly from that predicted for electron-phonon interactions. We show here that plasmons, important in the relaxation of energetic carriers in bulk semiconductors, can also provide a pathway for energy relaxation in transport experiments in graphene. We obtain a total loss rate to plasmons that results in energy relaxation times whose dependence on temperature and density closely matches that found experimentally.

  20. Nonlinear Relaxation in Population Dynamics

    Science.gov (United States)

    Cirone, Markus A.; de Pasquale, Ferdinando; Spagnolo, Bernardo

    We analyze the nonlinear relaxation of a complex ecosystem composed of many interacting species. The ecological system is described by generalized Lotka-Volterra equations with a multiplicative noise. The transient dynamics is studied in the framework of the mean field theory and with random interaction between the species. We focus on the statistical properties of the asymptotic behaviour of the time integral of the ith population and on the distribution of the population and of the local field.

  1. Structural relaxation: low temperature properties

    International Nuclear Information System (INIS)

    Cruz, F. de la

    1984-01-01

    We discuss the changes in transport and superconducting properties of amorphous Zr 70 Cu 30 , induced by thermal relaxation. The experimental results are used to investigate the relation between the microscopic parameters and the observed physical properties. It is shown that the density of eletronic states determines the shift Tc as well as the variation of the electrical resistivity. It is necessary to assume strong hybridization between s and d bands to understand the eletrodynamic response of the superconductor. (Author) [pt

  2. The Effects of Suggestibility on Relaxation.

    Science.gov (United States)

    Rickard, Henry C.; And Others

    1985-01-01

    Selected undergraduates (N=32) on the basis of Creative Imagination Scale scores and randomly assigned high and low suggestibility subjects to progressive relaxation (PR) and suggestions of relaxation (SR) training modes. Results revealed a significant pre-post relaxation effect, and main efffects for both suggestibility and training mode. (NRB)

  3. Relaxed Poisson cure rate models.

    Science.gov (United States)

    Rodrigues, Josemar; Cordeiro, Gauss M; Cancho, Vicente G; Balakrishnan, N

    2016-03-01

    The purpose of this article is to make the standard promotion cure rate model (Yakovlev and Tsodikov, ) more flexible by assuming that the number of lesions or altered cells after a treatment follows a fractional Poisson distribution (Laskin, ). It is proved that the well-known Mittag-Leffler relaxation function (Berberan-Santos, ) is a simple way to obtain a new cure rate model that is a compromise between the promotion and geometric cure rate models allowing for superdispersion. So, the relaxed cure rate model developed here can be considered as a natural and less restrictive extension of the popular Poisson cure rate model at the cost of an additional parameter, but a competitor to negative-binomial cure rate models (Rodrigues et al., ). Some mathematical properties of a proper relaxed Poisson density are explored. A simulation study and an illustration of the proposed cure rate model from the Bayesian point of view are finally presented. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Vibrational relaxation in OCS mixtures

    International Nuclear Information System (INIS)

    Simpson, C.J.S.M.; Gait, P.D.; Simmie, J.M.

    1976-01-01

    Experimental measurements are reported of vibrational relaxation times which may be used to show whether there is near resonant vibration-rotation energy transfer between OCS and H 2 , D 2 or HD. Vibrational relaxation times have been measured in OCS and OCS mixtures over the temperature range 360 to 1000 K using a shock tube and a laser schlieren system. The effectiveness of the additives in reducing the relaxation time of OCS is in the order 4 He 3 He 2 2 and HD. Along this series the effect of an increase in temperature changes from the case of speeding up the rate with 4 He to retarding it with D 2 , HD and H 2 . There is no measurable difference in the effectiveness of n-D 2 and o-D 2 and little, or no, difference between n-H 2 and p-H 2 . Thus the experimental results do not give clear evidence for rotational-vibration energy transfer between hydrogen and OCS. This contrasts with the situation for CO 2 + H 2 mixtures. (author)

  5. Relaxed plasma-vacuum systems

    International Nuclear Information System (INIS)

    Spies, G.O.; Lortz, D.; Kaiser, R.

    2001-01-01

    Taylor's theory of relaxed toroidal plasmas (states of lowest energy with fixed total magnetic helicity) is extended to include a vacuum between the plasma and the wall. In the extended variational problem, one prescribes, in addition to the helicity and the magnetic fluxes whose conservation follows from the perfect conductivity of the wall, the fluxes whose conservation follows from the assumption that the plasma-vacuum interface is also perfectly conducting (if the wall is a magnetic surface, then one has the toroidal and the poloidal flux in the vacuum). Vanishing of the first energy variation implies a pressureless free-boundary magnetohydrostatic equilibrium with a Beltrami magnetic field in the plasma, and in general with a surface current in the interface. Positivity of the second variation implies that the equilibrium is stable according to ideal magnetohydrodynamics, that it is a relaxed state according to Taylor's theory if the interface is replaced by a wall, and that the surface current is nonzero (at least if there are no closed magnetic field lines in the interface). The plane slab, with suitable boundary conditions to simulate a genuine torus, is investigated in detail. The relaxed state has the same double symmetry as the vessel if, and only if, the prescribed helicity is in an interval that depends on the prescribed fluxes. This interval is determined in the limit of a thin slab

  6. Regularized Label Relaxation Linear Regression.

    Science.gov (United States)

    Fang, Xiaozhao; Xu, Yong; Li, Xuelong; Lai, Zhihui; Wong, Wai Keung; Fang, Bingwu

    2018-04-01

    Linear regression (LR) and some of its variants have been widely used for classification problems. Most of these methods assume that during the learning phase, the training samples can be exactly transformed into a strict binary label matrix, which has too little freedom to fit the labels adequately. To address this problem, in this paper, we propose a novel regularized label relaxation LR method, which has the following notable characteristics. First, the proposed method relaxes the strict binary label matrix into a slack variable matrix by introducing a nonnegative label relaxation matrix into LR, which provides more freedom to fit the labels and simultaneously enlarges the margins between different classes as much as possible. Second, the proposed method constructs the class compactness graph based on manifold learning and uses it as the regularization item to avoid the problem of overfitting. The class compactness graph is used to ensure that the samples sharing the same labels can be kept close after they are transformed. Two different algorithms, which are, respectively, based on -norm and -norm loss functions are devised. These two algorithms have compact closed-form solutions in each iteration so that they are easily implemented. Extensive experiments show that these two algorithms outperform the state-of-the-art algorithms in terms of the classification accuracy and running time.

  7. Mechanical relaxation in chalcogenide glasses of the Ge-As-S system

    International Nuclear Information System (INIS)

    Bilanych, V.S.; Melnychenko, T.D.; Rizak, V.M.; Makauz, I.I.

    2006-01-01

    The temperature and frequency-related dependences of the internal friction and the shear modulus in Ge x As 40-x S 60 glasses have been studied. The maxima of internal friction of both the relaxation and non relaxation types have been found in the low-temperature range. A relaxation maximum has been revealed in the vitrification region, and its parameters have been determined. Possible mechanisms of these processes have been discussed

  8. Effects of thermal relaxation on an amorphous superconducting Zr--Rh alloy

    International Nuclear Information System (INIS)

    Drehman, A.J.; Johnson, W.L.

    1978-05-01

    The electronic and superconducting properties of an amorphous transition metal alloy are used to evaluate the effects of low temperature annealing. It is observed that the superconducting transition temperature and the electrical resistivity relax exponentially in time from their initial value to a final relaxed value. From this an activation energy for the relaxation process is derived and an explanation is suggested which involves internal stress

  9. Effect of iodine impurity on relaxation of photoexcited silver chloride

    International Nuclear Information System (INIS)

    Vostrikova, Yu. V.; Klyuev, V. G.

    2008-01-01

    The time and temperature dependences of relaxation of excited AgCl and AgCl:I crystals is studied by the method of photostimulated flash of luminescence. The presence of iodine impurity in silver chloride gives rise to hole recombination (luminescence) centers and hole traps in the band gap. It is shown that the main contribution to the decrease in the concentration of electrons localized at deep traps is made by the recombination of electrons with holes released thermally from shallow localization levels (iodine-related centers). Estimation of activation energy for the relaxation process showed that these energies for the AgCl and AgCl:I samples under study are the same within the experimental error and are equal to E rel1 = 0.01 ± 0.0005 eV for the initial stage of relaxation and E rel2 = 0.09 ± 0.005 eV for the final state. This fact indicates that the majority of hole traps involved in the relaxation process in AgCl are related to iodine impurity. In the course of thermal relaxation in AgCl, relocalization of nonequilibrium charge carriers from shallow levels to deep levels is observed. The depth of the corresponding trap is E arl = 0.174 ± 0.03 eV.

  10. 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.

  11. 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...

  12. 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.

  13. 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.

  14. Relaxation oscillations in stimulated Raman scattering

    International Nuclear Information System (INIS)

    Kachen, G.I.; Lowdermilk, W.H.

    1977-01-01

    Light pulses created by stimulated Raman scattering having been found to exhibit a complex time dependence which resembles relaxation oscillations. A focused laser pulse generated both forward and backward Raman emissions which appeared as a series of pulses with durations much shorter than the incident laser pulse. Time dependence of the Raman emission was observed directly by use of a streak camera. The number of observed pulses increased with the intensity of the incident pulse, while separation of the pulses in time depended on the length of the focal region. Beam focusing was incorporated in the coupled wave equations for stimulated Raman scattering. These rate equations were then solved numerically, and the results are in good qualitative agreement with the experimental observations. The short Raman pulses are created by a process associated with depletion of the incident laser pulse. This process occurs under a broad range of conditions

  15. Relaxation dynamics and thermophysical properties of vegetable oils using time-domain reflectometry.

    Science.gov (United States)

    Sonkamble, Anil A; Sonsale, Rahul P; Kanshette, Mahesh S; Kabara, Komal B; Wananje, Kunal H; Kumbharkhane, Ashok C; Sarode, Arvind V

    2017-04-01

    Dielectric relaxation studies of vegetable oils are important for insights into their hydrogen bonding and intermolecular dynamics. The dielectric relaxation and thermo physical properties of triglycerides present in some vegetable oils have been measured over the frequency range of 10 MHz to 7 GHz in the temperature region 25 to 10 °C using a time-domain reflectometry approach. The frequency and temperature dependence of dielectric constants and dielectric loss factors were determined for coconut, peanut, soya bean, sunflower, palm, and olive oils. The dielectric permittivity spectra for each of the studied vegetable oils are explained using the Debye model with their complex dielectric permittivity analyzed using the Havriliak-Negami equation. The dielectric parameters static permittivity (ε 0 ), high-frequency limiting static permittivity (ε ∞ ), average relaxation time (τ 0 ), and thermodynamic parameters such as free energy (∆F τ ), enthalpy (∆H τ ), and entropy of activation (∆S τ ) were also measured. Calculation and analysis of these thermodynamic parameters agrees with the determined dielectric parameters, giving insights into the temperature dependence of the molecular dynamics of these systems.

  16. Dynamics and relaxation in confined medium. Application to 129Xe magnetic relaxation in Vycor

    International Nuclear Information System (INIS)

    Pasquier, Virginie

    1995-01-01

    Porous media morphology and topology drive the exploration of pore space by fluid. So, analysis of transport process, associated with relaxation mechanism, allows indirect study of pore geometry. The purpose of this work is to understand better the relation between geometry and transport. This study involves two parts: a modelization and prediction step is followed by an experimental application of magnetic relaxation. Numerical simulations and analytical models allow to quantify the influence on the solid interface of the dynamical behavior of confined gas in disordered porous media (granular structure and porous network) or in common geometry (cylindrical and lamellar interfaces). The formalism of diffusion propagator is a powerful tool to quantify the influence of the pore geometry on the diffusion of confined gas. The propagator holds all dynamical information on the system; it also predicts the temporal evolution of the autocorrelation functions of the Hamiltonian describing local coupling. In an intermediate time scale, magnetic relaxation shows complex diffusional regime: the autocorrelation functions decrease in a power law with a exponent smaller than d/2 (where d is the Euclidian dimension of the system). This behavior is analogous to dynamic in low-dimensional space, but here arises from surface correlations of the porous media. The long-time behavior of the autocorrelation functions retrieves the asymptotic decrease t -d/2 . Moreover, atypical behavior is observed for the Knudsen diffusion between infinite planes. It turns out that 129 Xe NMR is a appropriate technique to characterize organization and diffusion of gas confined in Vycor. Systematic studies of temperature and pressure effect on the 129 Xe chemical shift allow to specify the Xe/solid interaction. The analysis of the relaxation measurements, thanks to the numerical development, confirms conclusions arising from the study of diffusion propagator. (author) [fr

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

    Science.gov (United States)

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

    2015-01-01

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

  18. 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.

  19. 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%

  20. The relationships between suggestibility, influenceability, and relaxability.

    Science.gov (United States)

    Polczyk, Romuald; Frey, Olga; Szpitalak, Malwina

    2013-01-01

    This research explores the relationships between relaxability and various aspects of suggestibility and influenceability. The Jacobson Progressive Muscle Relaxation procedure was used to induce relaxation. Tests of direct suggestibility, relating to the susceptibility of overt suggestions, and indirect suggestibility, referring to indirect hidden influence, as well as self-description questionnaires on suggestibility and the tendency to comply were used. Thayer's Activation-Deactivation Adjective Check List, measuring various kinds of activation and used as a pre- and posttest, determined the efficacy of the relaxation procedure. Indirect, direct, and self-measured suggestibility proved to be positively related to the ability to relax, measured by Thayer's subscales relating to emotions. Compliance was not related to relaxability. The results are discussed in terms of the aspects of relaxation training connected with suggestibility.

  1. Hydrodynamic relaxations in dissipative particle dynamics

    Science.gov (United States)

    Hansen, J. S.; Greenfield, Michael L.; Dyre, Jeppe C.

    2018-01-01

    This paper studies the dynamics of relaxation phenomena in the standard dissipative particle dynamics (DPD) model [R. D. Groot and P. B. Warren, J. Chem. Phys. 107, 4423 (1997)]. Using fluctuating hydrodynamics as the framework of the investigation, we focus on the collective transverse and longitudinal dynamics. It is shown that classical hydrodynamic theory predicts the transverse dynamics at relatively low temperatures very well when compared to simulation data; however, the theory predictions are, on the same length scale, less accurate for higher temperatures. The agreement with hydrodynamics depends on the definition of the viscosity, and here we find that the transverse dynamics are independent of the dissipative and random shear force contributions to the stress. For high temperatures, the spectrum for the longitudinal dynamics is dominated by the Brillouin peak for large length scales and the relaxation is therefore governed by sound wave propagation and is athermal. This contrasts the results at lower temperatures and small length scale, where the thermal process is clearly present in the spectra. The DPD model, at least qualitatively, re-captures the underlying hydrodynamical mechanisms, and quantitative agreement is excellent at intermediate temperatures for the transverse dynamics.

  2. Low temperature dielectric relaxation and charged defects in ferroelectric thin films

    Directory of Open Access Journals (Sweden)

    A. Artemenko

    2013-04-01

    Full Text Available We report a dielectric relaxation in BaTiO3-based ferroelectric thin films of different composition and with several growth modes: sputtering (with and without magnetron and sol-gel. The relaxation was observed at cryogenic temperatures (T < 100 K for frequencies from 100 Hz up to 10 MHz. This relaxation activation energy is always lower than 200 meV and is very similar to the relaxation that we reported in the parent bulk perovskites. Based on our Electron Paramagnetic Resonance (EPR investigation, we ascribe this dielectric relaxation to the hopping of electrons among Ti3+-V(O charged defects. Being dependent on the growth process and on the amount of oxygen vacancies, this relaxation can be a useful probe of defects in actual integrated capacitors with no need for specific shaping.

  3. Internal structures of self-organized relaxed states and self-similar decay phase

    International Nuclear Information System (INIS)

    Kondoh, Yoshiomi

    1992-03-01

    A thought analysis on relaxation due to nonlinear processes is presented to lead to a set of general thoughts applicable to general nonlinear dynamical systems for finding out internal structures of the self-organized relaxed state without using 'invariant'. Three applications of the set of general thoughts to energy relaxations in resistive MHD plasmas, incompressible viscous fluids, and incompressible viscous MHD fluids are shown to lead to the internal structures of the self-organized relaxed states. It is shown that all of the relaxed states in these three dynamical systems are followed by self-similar decay phase without significant change of the spatial structure. The well known relaxed state of ∇ x B = ±λ B is shown to be derived generally in the low β plasma limit. (author)

  4. Slowing hot-carrier relaxation in graphene using a magnetic field

    Science.gov (United States)

    Plochocka, P.; Kossacki, P.; Golnik, A.; Kazimierczuk, T.; Berger, C.; de Heer, W. A.; Potemski, M.

    2009-12-01

    A degenerate pump-probe technique is used to investigate the nonequilibrium carrier dynamics in multilayer graphene. Two distinctly different dynamics of the carrier relaxation are observed. A fast relaxation (˜50fs) of the carriers after the initial effect of phase-space filling followed by a slower relaxation (˜4ps) due to thermalization. Both relaxation processes are less efficient when a magnetic field is applied at low temperatures which is attributed to the suppression of the electron-electron Auger scattering due to the nonequidistant Landau-level spacing of the Dirac fermions in graphene.

  5. Compaction and relaxation of biofilms

    KAUST Repository

    Valladares Linares, R.

    2015-06-18

    Operation of membrane systems for water treatment can be seriously hampered by biofouling. A better characterization of biofilms in membrane systems and their impact on membrane performance may help to develop effective biofouling control strategies. The objective of this study was to determine the occurrence, extent and timescale of biofilm compaction and relaxation (decompaction), caused by permeate flux variations. The impact of permeate flux changes on biofilm thickness, structure and stiffness was investigated in situ and non-destructively with optical coherence tomography using membrane fouling monitors operated at a constant crossflow velocity of 0.1 m s−1 with permeate production. The permeate flux was varied sequentially from 20 to 60 and back to 20 L m−2 h−1. The study showed that the average biofilm thickness on the membrane decreased after elevating the permeate flux from 20 to 60 L m−2 h−1 while the biofilm thickness increased again after restoring the original flux of 20 L m−2 h−1, indicating the occurrence of biofilm compaction and relaxation. Within a few seconds after the flux change, the biofilm thickness was changed and stabilized, biofilm compaction occurred faster than the relaxation after restoring the original permeate flux. The initial biofilm parameters were not fully reinstated: the biofilm thickness was reduced by 21%, biofilm stiffness had increased and the hydraulic biofilm resistance was elevated by 16%. Biofilm thickness was related to the hydraulic biofilm resistance. Membrane performance losses are related to the biofilm thickness, density and morphology, which are influenced by (variations in) hydraulic conditions. A (temporarily) permeate flux increase caused biofilm compaction, together with membrane performance losses. The impact of biofilms on membrane performance can be influenced (increased and reduced) by operational parameters. The article shows that a (temporary) pressure increase leads to more

  6. 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

  7. 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.

  8. 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

  9. Anomalous behavior of secondary dielectric relaxation in polypropylene glycols

    Energy Technology Data Exchange (ETDEWEB)

    Grzybowska, K; Grzybowski, A; Ziolo, J; Rzoska, S J; Paluch, M [Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice (Poland)

    2007-09-19

    A surprising slow down in the dielectric secondary {gamma}-relaxation with temperature increasing near the glass transition is confirmed for several polypropylene glycols. The peculiar behavior diminishes as the molecular weight grows. The minimal model (Dyre and Olsen 2003 Phys. Rev. Lett. 91 155703) is applied successfully to describe the temperature dependences of the {gamma}-relaxation times. The minimal model parameters are analyzed for different molecular weights. A molecular explanation of the {gamma}-process anomaly for polypropylene glycols is proposed on the basis of the minimal model prediction.

  10. Non-exponential dynamic relaxation in strongly nonequilibrium nonideal plasmas

    International Nuclear Information System (INIS)

    Morozov, I V; Norman, G E

    2003-01-01

    Relaxation of kinetic energy to the equilibrium state is simulated by the molecular dynamics method for nonideal two-component non-degenerate plasmas. Three limiting examples of initial states of strongly nonequilibrium plasma are considered: zero electron velocities, zero ion velocities and zero velocities of both electrons and ions. The initial non-exponential stage, its duration τ nB and subsequent exponential stages of the relaxation process are studied for a wide range of the nonideality parameter and the ion mass

  11. Characterization of structural relaxation in inorganic glasses using length dilatometry

    Science.gov (United States)

    Koontz, Erick

    The processes that govern how a glass relaxes towards its thermodynamic quasi-equilibrium state are major factors in understanding glass behavior near the glass transition region, as characterized by the glass transition temperature (Tg). Intrinsic glass properties such as specific volume, enthalpy, entropy, density, etc. are used to map the behavior of the glass network below in and near the transition region. The question of whether a true thermodynamic second order phase transition takes place in the glass transition region is another pending question. Linking viscosity behavior to entropy, or viewing the glass configuration as an energy landscape are just a couple of the most prevalent methods used for attempting to understand the glass transition. The structural relaxation behavior of inorganic glasses is important for more than scientific reasons, many commercial glass processing operations including glass melting and certain forms of optical fabrication include significant time spent in the glass transition region. For this reason knowledge of structural relaxation processes can, at a minimum, provide information for annealing duration of melt-quenched glasses. The development of a predictive model for annealing time prescription has the potential to save glass manufacturers significant time and money as well as increasing volume throughput. In optical hot forming processes such as precision glass molding, molded optical components can significantly change in shape upon cooling through the glass transition. This change in shape is not scientifically predictable as of yet though manufacturers typically use empirical rules developed in house. The classification of glass behavior in the glass transition region would allow molds to be accurately designed and save money for the producers. The work discussed in this dissertation is comprised of the development of a dilatometric measurement and characterization method of structural relaxation. The measurement and

  12. Thermally induced magnetic relaxation in square artificial spin ice

    Science.gov (United States)

    Andersson, M. S.; Pappas, S. D.; Stopfel, H.; Östman, E.; Stein, A.; Nordblad, P.; Mathieu, R.; Hjörvarsson, B.; Kapaklis, V.

    2016-11-01

    The properties of natural and artificial assemblies of interacting elements, ranging from Quarks to Galaxies, are at the heart of Physics. The collective response and dynamics of such assemblies are dictated by the intrinsic dynamical properties of the building blocks, the nature of their interactions and topological constraints. Here we report on the relaxation dynamics of the magnetization of artificial assemblies of mesoscopic spins. In our model nano-magnetic system - square artificial spin ice - we are able to control the geometrical arrangement and interaction strength between the magnetically interacting building blocks by means of nano-lithography. Using time resolved magnetometry we show that the relaxation process can be described using the Kohlrausch law and that the extracted temperature dependent relaxation times of the assemblies follow the Vogel-Fulcher law. The results provide insight into the relaxation dynamics of mesoscopic nano-magnetic model systems, with adjustable energy and time scales, and demonstrates that these can serve as an ideal playground for the studies of collective dynamics and relaxations.

  13. Nuclear magnetic relaxation of methyl group in liquids

    International Nuclear Information System (INIS)

    Blicharska, B.

    1986-01-01

    The theoretical description of the relaxation process of methyl group in liquids and some results of the measurements of relaxation function and relaxation times for cryoprotective solutions are presented. Starting from the application of the operator formalism the general equation for spin operators e.g. components of the nuclear spin and magnetization is founded. Next, the spin Hamiltonian is presented as contraction of the symmetry adapted spherical tensors as well as the correlation functions and spectral densities. On the basis of extended and modified Woessner model of motion the correlation functions and spectral densities are calculated for methyl group in liquids. Using these functions the relaxation matrix elements, the spin-spin and spin-lattice relaxation times can be expressed. The prediction of the theory agrees with author's previous experiments on cryoprotective solutions. The observed dependence on temperature, frequency and isotopic dilution in methanol-water, methanol-dimethyl sulfoxide (DMSO) and DMSO-water solutions is in a satisfactory agreement with theoretical equations. 34 refs. (author)

  14. Energy equation for the analysis of magnetization relaxation to equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Bertotti, G. [IEN Galileo Ferraris, Materials Department, Strada delle Cacce, 91, I-10135 Torino (Italy)]. E-mail: bertotti@ien.it; Bonin, R. [Dipartimento di Fisica, Politecnico di Torino, I-10129 Torino (Italy); Magni, A. [IEN Galileo Ferraris, Materials Department, Strada delle Cacce, 91, I-10135 Torino (Italy); Mayergoyz, I.D. [Department of Electrical and Computer Engineering, University of Maryland, College Park, Maryland, 20742 (United States); Serpico, C. [Dipartimento di Ingegneria Elettrica, Universita di Napoli ' Federico II' , I-80125 Naples (Italy)

    2005-02-01

    Magnetization relaxation starting from a generic non-equilibrium state is analytically described. An equation for the energy decay is obtained. On this basis, an approximate expression for the magnetization motion during the ringing process is obtained in terms of Jacobi elliptic functions with time-dependent parameters.

  15. Energy equation for the analysis of magnetization relaxation to equilibrium

    International Nuclear Information System (INIS)

    Bertotti, G.; Bonin, R.; Magni, A.; Mayergoyz, I.D.; Serpico, C.

    2005-01-01

    Magnetization relaxation starting from a generic non-equilibrium state is analytically described. An equation for the energy decay is obtained. On this basis, an approximate expression for the magnetization motion during the ringing process is obtained in terms of Jacobi elliptic functions with time-dependent parameters

  16. A model for the generic alpha relaxation in viscous liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    2005-01-01

    Dielectric measurements on molecular liquids just above the glass transition indicate that alpha relaxation is characterized by a generic high-frequency loss varying as one over square root of frequency, whereas deviations from this come from one or more low-lying beta processes [Olsen et al., Phys...

  17. Detection of quadrupole relaxation in an optically pumped cesium vapour

    Energy Technology Data Exchange (ETDEWEB)

    Bernabeu, E; Tornos, J

    1985-10-01

    The relaxation of quadrupole orientation induced by means of optical pumping in a cesium vapour is experimentally studied, and the results are compared to the theoretical predictions. The optical detection process of this type of orientation is also discussed as a function of the polarization and spectral profile of the detection light.

  18. Stability and suppression of turbulence in relaxing molecular gas flows

    CERN Document Server

    Grigoryev, Yurii N

    2017-01-01

    This book presents an in-depth systematic investigation of a dissipative effect which manifests itself as the growth of hydrodynamic stability and suppression of turbulence in relaxing molecular gas flows. The work describes the theoretical foundations of a new way to control stability and laminar turbulent transitions in aerodynamic flows. It develops hydrodynamic models for describing thermal nonequilibrium gas flows which allow the consideration of suppression of inviscid acoustic waves in 2D shear flows. Then, nonlinear evolution of large-scale vortices and Kelvin-Helmholtz waves in relaxing shear flows are studied. Critical Reynolds numbers in supersonic Couette flows are calculated analytically and numerically within the framework of both linear and nonlinear classical energy hydrodynamic stability theories. The calculations clearly show that the relaxation process can appreciably delay the laminar-turbulent transition. The aim of the book is to show the new dissipative effect, which can be used for flo...

  19. Wall relaxation and the driving forces for cell expansive growth

    Science.gov (United States)

    Cosgrove, D. J.

    1987-01-01

    When water uptake by growing cells is prevented, the turgor pressure and the tensile stress in the cell wall are reduced by continued wall loosening. This process, termed in vivo stress relaxation, provides a new way to study the dynamics of wall loosening and to measure the wall yield threshold and the physiological wall extensibility. Stress relaxation experiments indicate that wall stress supplies the mechanical driving force for wall yielding. Cell expansion also requires water absorption. The driving force for water uptake during growth is created by wall relaxation, which lowers the water potential of the expanding cells. New techniques for measuring this driving force show that it is smaller than believed previously; in elongating stems it is only 0.3 to 0.5 bar. This means that the hydraulic resistance of the water transport pathway is small and that rate of cell expansion is controlled primarily by wall loosening and yielding.

  20. Stability investigations of relaxing molecular gas flows. Results and perspectives

    Science.gov (United States)

    Grigor'ev, Yurii N.; Ershov, Igor V.

    2017-10-01

    This article presents results of systematic investigations of a dissipative effect which manifests itself as the growth of hydrodynamic stability and suppression of turbulence in relaxing molecular gas flows. The effect can be a new way for control stability and laminar turbulent transition in aerodynamic flows. The consideration of suppression of inviscid acoustic waves in 2D shear flows is presented. Nonlinear evolution of large-scale vortices and Kelvin — Helmholtz waves in relaxing shear flows are studied. Critical Reynolds numbers in supersonic Couette flows are calculated analytically and numerically within the framework of both classical linear and nonlinear energy hydrodynamic stability theories. The calculations clearly show that the relaxation process can appreciably delay the laminar-turbulent transition. The aim of this article is to show the new dissipative effect, which can be used for flow control and laminarization.

  1. Dielectric relaxations above room temperature in DMPU derived polyaniline film

    International Nuclear Information System (INIS)

    Mallya, Ashwini N.; Yashavanth Kumar, G.S.; Ranjan, Rajeev; Ramamurthy, Praveen C.

    2012-01-01

    Dielectric measurements carried out on drop casted from solution of emeraldine base form of polyaniline films in the temperature range 30-300 °C revealed occurrence of two maxima in the loss tangent as a function of temperature. The activation energies corresponding to these two relaxation processes were found to be ∼0.5 eV and ∼1.5 eV. The occurrence of one relaxation peak in the dispersion curve of the imaginary part of the electric modulus suggests the absence of microphase separation in the film. Thermogravimetric analysis and infrared spectroscopic measurements showed that the films retained its integrity up to 300 °C. The dielectric relaxation at higher temperatures with large activation energy of 1.5 eV is attributed to increase in the barrier potential due to decrease in the polymer conjugation as a result of wide amplitude motion of the chain segments well above the glass transition temperature.

  2. 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.

  3. Rotation and scale change invariant point pattern relaxation matching by the Hopfield neural network

    Science.gov (United States)

    Sang, Nong; Zhang, Tianxu

    1997-12-01

    Relaxation matching is one of the most relevant methods for image matching. The original relaxation matching technique using point patterns is sensitive to rotations and scale changes. We improve the original point pattern relaxation matching technique to be invariant to rotations and scale changes. A method that makes the Hopfield neural network perform this matching process is discussed. An advantage of this is that the relaxation matching process can be performed in real time with the neural network's massively parallel capability to process information. Experimental results with large simulated images demonstrate the effectiveness and feasibility of the method to perform point patten relaxation matching invariant to rotations and scale changes and the method to perform this matching by the Hopfield neural network. In addition, we show that the method presented can be tolerant to small random error.

  4. Stress relaxation experiments on a lamellar polystyrene-polyisoprene diblock copolymer melt

    DEFF Research Database (Denmark)

    Holmqvist, P.; Castelletto, V.; Hamley, I.W.

    2001-01-01

    The non-linear rheology of the lamellar phase of a polystyrene-polyisoprene diblock copolymer is studied by oscillatory shear experiments. The relaxation of the shear modulus, G(t, gamma) is studied as a function of strain amplitude, gamma, up to large amplitude strains, gamma = 100%. The decay...... of G(t, gamma) is analysed using the model-independent CONTIN inverse Laplace transform algorithm to obtain a series of relaxation times, which reveals multiple relaxation processes. The timescale for the fastest relaxation processes is compared to those previously observed for diblock copolymer melts...... via dynamic light scattering experiments. The slowest relaxation process may be related to the shear-induced orientation of the lamellae. It is shown that time-strain separability G(t, gamma)= G(t)h(gamma) can be applied, and the damping function h(gamma) is consistent with a strongly strain...

  5. Glass transition and relaxation dynamics of propylene glycol-water solutions confined in clay

    Science.gov (United States)

    Elamin, Khalid; Björklund, Jimmy; Nyhlén, Fredrik; Yttergren, Madeleine; Mârtensson, Lena; Swenson, Jan

    2014-07-01

    The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the α-relaxation

  6. Post-seismic relaxation from geodetic and seismic data

    Directory of Open Access Journals (Sweden)

    Mikhail V. Rodkin

    2017-01-01

    Full Text Available We have examined the aftershock sequence and the post-seismic deformation process of the Parkfield earthquake (2004, M = 6, California, USA source area using GPS data. This event was chosen because of the possibility of joint analysis of data from the rather dense local GPS network (from SOPAC Internet archive and of the availability of the rather detailed aftershock sequence data (http://www.ncedc.org/ncedc/catalog-search.html. The relaxation process of post-seismic deformation prolongs about the same 400 days as the seismic aftershock process does. Thus, the aftershock process and the relaxation process in deformation could be the different sides of the same process. It should be noted that the ratio of the released seismic energy and of the GPS obtained deformation is quite different for the main shock and for the aftershock stage. The ratio of the released seismic energy to the deformation value decreases essentially for the post-shock process. The similar change in the seismic energy/deformation value ratio is valid in a few other strong earthquakes. Thus, this decrease seems typical of aftershock sequences testifying for decrease of ratio of elastic to inelastic deformation in the process of post-shock relaxation when the source area appears to be mostly fractured after the main shock occurs, but the healing process had no yet sufficient time to develop.

  7. Cherenkov and anomalous Doppler effects in the relaxation of an electron beam

    International Nuclear Information System (INIS)

    Muschietti, L.; Appert, K.; Vaclavik, J.

    1981-01-01

    The interplay between the Cherenkov and anomalous Doppler interactions in the relaxation of a warm electron beam is investigated by numerical means. The most important feature in the interplay is found to be a nonelastic isotropization. A simple semianalytical model which allows one to estimate various quantities relevant to the relaxation process is also presented

  8. Ultrasonic relaxations in borate glasses

    International Nuclear Information System (INIS)

    D'Angelo, G.; Tripodo, G.; Carini, G.; Cosio, E.; Bartolotta, A.; Di Marco, G.

    2004-01-01

    The attenuation and velocity of ultrasonic waves of frequencies in the range from 10 to 70 MHz have been measured in M 2 O-B 2 O 3 borate glasses (M: Li or Ag) as a function of temperature between 15 and 350 K. The velocity of sound waves decreases with increasing temperature in all the glasses, the decrease as the temperature is increased is larger in glasses containing silver than in those with lithium. A broad relaxation peak characterises the attenuation behaviour of the lithium and silver borate glasses at temperatures below 100 K and is paralleled by a corresponding dispersive behaviour of the sound velocity. Above 100 K, the ultrasonic velocity shows a nearly linear behaviour regulated by the vibrational anharmonicity, which decreases with increasing content of modifier oxide and is smaller in lithium than in silver borates. These results suggest that the relaxation of structural defects and the anharmonicity of borate glasses are strongly affected by two parameters: the number of bridging bonds per network forming ion and the polarising power of network modifier ions which occupy sites in the existing interstices

  9. Statistical mechanics of violent relaxation

    International Nuclear Information System (INIS)

    Shu, F.H.

    1978-01-01

    We reexamine the foundations of Lynden-Bell's statistical mechanical discussion of violent relaxation in collisionless stellar systems. We argue that Lynden-Bell's formulation in terms of a continuum description introduces unnecessary complications, and we consider a more conventional formulation in terms of particles. We then find the exclusion principle discovered by Lynden-Bell to be quantitatively important only at phase densities where two-body encounters are no longer negligible. Since the edynamical basis for the exclusion principle vanishes in such cases anyway, Lynden-Bell statistics always reduces in practice to Maxwell-Boltzmann statistics when applied to stellar systems. Lynden-Bell also found the equilibrium distribution function generally to be a sum of Maxwellians with velocity dispersions dependent on the phase density at star formation. We show that this difficulty vanishes in the particulate description for an encounterless stellar system as long as stars of different masses are initially well mixed in phase space. Our methods also demonstrate the equivalence between Gibbs's formalism which uses the microcanonical ensemble and Boltzmann's formalism which uses a coarse-grained continuum description. In addition, we clarify the concept of irreversible behavior on a macroscopic scale for an encounterless stellar system. Finally, we comment on the use of unusual macroscopic constraints to simulate the effects of incomplete relaxation

  10. Comparison between the results of stress relaxation - and creep tests in a stainless steel 316 at 8000C

    International Nuclear Information System (INIS)

    Miranda, P.E.V. de.

    1978-07-01

    A sequence of stress relaxation tests from the same initial stress showed an estabilization of the relaxed fraction of stress of a 316 stainless steel at 800 0 C. This represents the exhaustion of the deformation process of the material at this temperature. Results from the relaxation tests were obtained by utilizing a recently proposed model. The slope in from the log epsilon sup(.) x logσ/E curve obtained by relaxation (n = 6,80) closely matched that determined by creep tests (n = 6,50). This presents a possibility of determined by stress relaxation of the parameters usually calculated by creep. (Author) [pt

  11. Paramagnetic relaxation effects in perturbed angular correlations for arbitrary electronic relaxation time

    International Nuclear Information System (INIS)

    Chopin, C.; Spanjaard, D.; Hartmann-Boutron, F.

    1975-01-01

    Previous perturbation treatments of paramagnetic relaxation effects in γγ PAC were limited to the case of very short electronic relaxation times. This limitation is circumvented by invoking a new perturbation theory recently elaborated by Hirst and others for handling relaxation effects in Moessbauer spectra. Under the assumption of spherical electronic relaxation the perturbation factors are computed as functions of certain relaxation parameters which are directly related to the microscopic relaxation Hamiltonian. The results are compared to those of the stochastic theory of Scherer and Blume [fr

  12. Suppression of Raman electron spin relaxation of radicals in crystals. Comparison of Cu2+ and free radical relaxation in triglycine sulfate and Tutton salt single crystals.

    Science.gov (United States)

    Hoffmann, S K; Goslar, J; Lijewski, S

    2011-08-31

    Electron spin-lattice relaxation was measured by the electron spin echo method in a broad temperature range above 4.2 K for Cu(2+) ions and free radicals produced by ionizing radiation in triglycine sulfate (TGS) and Tutton salt (NH4)(2)Zn(SO4)2 ⋅ 6H2O crystals. Localization of the paramagnetic centres in the crystal unit cells was determined from continuous wave electron paramagnetic resonance spectra. Various spin relaxation processes and mechanisms are outlined. Cu(2+) ions relax fast via two-phonon Raman processes in both crystals involving the whole phonon spectrum of the host lattice. This relaxation is slightly slower for TGS where Cu(2+) ions are in the interstitial position. The ordinary Raman processes do not contribute to the radical relaxation which relaxes via the local phonon mode. The local mode lies within the acoustic phonon band for radicals in TGS but within the optical phonon range in (NH4)(2)Zn(SO4)2 ⋅ 6H2O. In the latter the cross-relaxation was considered. A lack of phonons around the radical molecules suggested a local crystal amorphisation produced by x- or γ-rays.

  13. Cross relaxation in nitroxide spin labels

    DEFF Research Database (Denmark)

    Marsh, Derek

    2016-01-01

    Cross relaxation, and mI-dependence of the intrinsic electron spin-lattice relaxation rate We, are incorporated explicitly into the rate equations for the electron-spin population differences that govern the saturation behaviour of 14N- and 15N-nitroxide spin labels. Both prove important in spin......-label EPR and ELDOR, particularly for saturation recovery studies. Neither for saturation recovery, nor for CW-saturation EPR and CW-ELDOR, can cross relaxation be described simply by increasing the value of We, the intrinsic spin-lattice relaxation rate. Independence of the saturation recovery rates from...... the hyperfine line pumped or observed follows directly from solution of the rate equations including cross relaxation, even when the intrinsic spin-lattice relaxation rate We is mI-dependent....

  14. 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.

  15. 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

  16. Structural relaxation in annealed hyperquenched basaltic glasses

    DEFF Research Database (Denmark)

    Guo, Xiaoju; Mauro, John C.; Potuzak, M.

    2012-01-01

    The enthalpy relaxation behavior of hyperquenched (HQ) and annealed hyperquenched (AHQ) basaltic glass is investigated through calorimetric measurements. The results reveal a common onset temperature of the glass transition for all the HQ and AHQ glasses under study, indicating that the primary...... relaxation is activated at the same temperature regardless of the initial departure from equilibrium. The analysis of secondary relaxation at different annealing temperatures provides insights into the enthalpy recovery of HQ glasses....

  17. Dielectric Relaxation of Water: Theory and Experiment

    International Nuclear Information System (INIS)

    Adhikari, Narayan Prasad; Paudyal, Harihar; Johri, Manoj

    2010-06-01

    We have studied the hydrogen bond dynamics and methods for evaluation of probability and relaxation time for hydrogen bond network. Further, dielectric relaxation time has been calculated by using a diagonalization procedure by obtaining eigen values (inverse of relaxation time) of a master equation framed on the basis of Fokker-Planck equations. Microwave cavity spectrometer has been described to make measurements of relaxation time. Slater's perturbation equations are given for the analysis of the data. A comparison of theoretical and experimental data shows that there is a need for improvements in the theoretical model and experimental techniques to provide exact information about structural properties of water. (author)

  18. Pair plasma relaxation time scales.

    Science.gov (United States)

    Aksenov, A G; Ruffini, R; Vereshchagin, G V

    2010-04-01

    By numerically solving the relativistic Boltzmann equations, we compute the time scale for relaxation to thermal equilibrium for an optically thick electron-positron plasma with baryon loading. We focus on the time scales of electromagnetic interactions. The collisional integrals are obtained directly from the corresponding QED matrix elements. Thermalization time scales are computed for a wide range of values of both the total-energy density (over 10 orders of magnitude) and of the baryonic loading parameter (over 6 orders of magnitude). This also allows us to study such interesting limiting cases as the almost purely electron-positron plasma or electron-proton plasma as well as intermediate cases. These results appear to be important both for laboratory experiments aimed at generating optically thick pair plasmas as well as for astrophysical models in which electron-positron pair plasmas play a relevant role.

  19. Relaxing Chosen-Ciphertext Security

    DEFF Research Database (Denmark)

    Canetti, Ran; Krawczyk, Hugo; Nielsen, Jesper Buus

    2003-01-01

    Security against adaptive chosen ciphertext attacks (or, CCA security) has been accepted as the standard requirement from encryption schemes that need to withstand active attacks. In particular, it is regarded as the appropriate security notion for encryption schemes used as components within...... general protocols and applications. Indeed, CCA security was shown to suffice in a large variety of contexts. However, CCA security often appears to be somewhat too strong: there exist encryption schemes (some of which come up naturally in practice) that are not CCA secure, but seem sufficiently secure...... “for most practical purposes.” We propose a relaxed variant of CCA security, called Replayable CCA (RCCA) security. RCCA security accepts as secure the non-CCA (yet arguably secure) schemes mentioned above; furthermore, it suffices for most existing applications of CCA security. We provide three...

  20. Diffusion in confinement as a microscopic relaxation mechanism in glass-forming liquids

    International Nuclear Information System (INIS)

    Mamontov, Eugene

    2012-01-01

    Using quasielastic neutron scattering, we compare dynamics in single-element liquids, glass-forming selenium and non glass-forming gallium. There is a single jump-diffusion process in gallium, whereas in selenium there is also a faster, spatially localized process. The fast and slow processes describe β- and α-relaxation, respectively. We then analyze an archetypical glass-former, glycerol, to show that the two-component fit, with β- and α-relaxations explicitly separated, yields the correct value for the translational diffusion coefficient and provides information on the spatial localization of the β-relaxation that is not experimentally accessible otherwise.

  1. 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)

  2. 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.

  3. 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.

  4. Spin-lattice relaxation of individual solid-state spins

    Science.gov (United States)

    Norambuena, A.; Muñoz, E.; Dinani, H. T.; Jarmola, A.; Maletinsky, P.; Budker, D.; Maze, J. R.

    2018-03-01

    Understanding the effect of vibrations on the relaxation process of individual spins is crucial for implementing nanosystems for quantum information and quantum metrology applications. In this work, we present a theoretical microscopic model to describe the spin-lattice relaxation of individual electronic spins associated to negatively charged nitrogen-vacancy centers in diamond, although our results can be extended to other spin-boson systems. Starting from a general spin-lattice interaction Hamiltonian, we provide a detailed description and solution of the quantum master equation of an electronic spin-one system coupled to a phononic bath in thermal equilibrium. Special attention is given to the dynamics of one-phonon processes below 1 K where our results agree with recent experimental findings and analytically describe the temperature and magnetic-field scaling. At higher temperatures, linear and second-order terms in the interaction Hamiltonian are considered and the temperature scaling is discussed for acoustic and quasilocalized phonons when appropriate. Our results, in addition to confirming a T5 temperature dependence of the longitudinal relaxation rate at higher temperatures, in agreement with experimental observations, provide a theoretical background for modeling the spin-lattice relaxation at a wide range of temperatures where different temperature scalings might be expected.

  5. Magnon interaction and relaxation in yttrium iron garnet

    International Nuclear Information System (INIS)

    Mukimov, K.M.; Jumaev, M.R.; Kenjaev, Z.M.

    2007-01-01

    Full text: Magnon interaction and relaxation are the fundamental characteristics describing the response of any system to an external AC field. Almost all experiments aimed at magnon excitation have been carried out in the microwave frequency range where only magnons with energies 0.1 - 5 K can be excited. Nevertheless, all magnons with energy lower or order of the temperature are involved in the processes of low energy magnon relaxation. The present study deals with the interactions of magnons in YIG in thermodynamic equilibrium at temperatures up to 300 K. We consider the exchange and magnetic - dipole terms in the YIG Hamiltonian and a term due to the local uniaxial crystallographic anisotropy, find the corresponding amplitudes of three - and four - magnon process, and calculate the relaxation rate and the correction to the ferromagnon frequency to the first order in the interaction. This correction is positive, in contrast to the case of ferromagnets, and it is proportional to at temperatures up to, in agreement with experiment. The exchange - relaxation rate of the magnons is found as a function of the wave vector and temperature. In the region this rate agrees with the familiar expression for ferromagnets. At higher temperatures, at which the main contribution to the exchange damping is from the magnons of the linear part of the spectrum, the temperature dependence of the damping becomes stronger. (authors)

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

    International Nuclear Information System (INIS)

    Simperler, A.

    1999-03-01

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

  7. 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...

  8. 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.

  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. 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.

  11. The Effects of Progressive Relaxation and Music on Attention, Relaxation, and Stress Responses: An Investigation of the Cognitive-Behavioral Model of Relaxation

    National Research Council Canada - National Science Library

    Scheufele, Peter

    1999-01-01

    ...) suggested that stress management techniques have specific effects A compromise position suggests that the specific effects of relaxation techniques are superimposed upon a general relaxation response...

  12. Lifshitz quasinormal modes and relaxation from holography

    NARCIS (Netherlands)

    Sybesma, Watse|info:eu-repo/dai/nl/369283074; Vandoren, Stefan|info:eu-repo/dai/nl/304830739

    2015-01-01

    We obtain relaxation times for field theories with Lifshitz scaling and with holographic duals Einstein-Maxwell-Dilaton gravity theories. This is done by computing quasinormal modes of a bulk scalar field in the presence of Lifshitz black branes. We determine the relation between relaxation time and

  13. Superparamagnetic relaxation of weakly interacting particles

    DEFF Research Database (Denmark)

    Mørup, Steen; Tronc, Elisabeth

    1994-01-01

    The influence of particle interactions on the superparamagnetic relaxation time has been studied by Mossbauer spectroscopy in samples of maghemite (gamma-Fe2O3) particles with different particle sizes and particle separations. It is found that the relaxation time decreases with decreasing particl...

  14. Models of Flux Tubes from Constrained Relaxation

    Indian Academy of Sciences (India)

    tribpo

    J. Astrophys. Astr. (2000) 21, 299 302. Models of Flux Tubes from Constrained Relaxation. Α. Mangalam* & V. Krishan†, Indian Institute of Astrophysics, Koramangala,. Bangalore 560 034, India. *e mail: mangalam @ iiap. ernet. in. † e mail: vinod@iiap.ernet.in. Abstract. We study the relaxation of a compressible plasma to ...

  15. Superparamagnetic relaxation in alpha-Fe particles

    DEFF Research Database (Denmark)

    Bødker, Franz; Mørup, Steen; Pedersen, Michael Stanley

    1998-01-01

    The superparamagnetic relaxation time of carbon-supported alpha-Fe particles with an average size of 3.0 Mm has been studied over a large temperature range by the use of Mossbauer spectroscopy combined with AC and DC magnetization measurements. It is found that the relaxation time varies...

  16. Baryogenesis via Elementary Goldstone Higgs Relaxation

    DEFF Research Database (Denmark)

    Gertov, Helene; Pearce, Lauren; Sannino, Francesco

    2016-01-01

    We extend the relaxation mechanism to the Elementary Goldstone Higgs framework. Besides studying the allowed parameter space of the theory we add the minimal ingredients needed for the framework to be phenomenologically viable. The very nature of the extended Higgs sector allows to consider very ...... but radiatively generated, it is possible to generate the observed matter-antimatter asymmetry via the relaxation mechanism....

  17. Relaxation dynamics following transition of solvated electrons

    International Nuclear Information System (INIS)

    Barnett, R.B.; Landman, U.; Nitzan, A.

    1989-01-01

    Relaxation dynamics following an electronic transition of an excess solvated electron in clusters and in bulk water is studied using an adiabatic simulation method. In this method the solvent evolves classically and the electron is constrained to a specified state. The coupling between the solvent and the excess electron is evaluated via the quantum expectation value of the electron--water molecule interaction potential. The relaxation following excitation (or deexcitation) is characterized by two time scales: (i) a very fast (/similar to/20--30 fs) one associated with molecular rotations in the first solvation shell about the electron, and (ii) a slower stage (/similar to/200 fs), which is of the order of the longitudinal dielectric relaxation time. The fast relaxation stage exhibits an isotope effect. The spectroscopical consequences of the relaxation dynamics are discussed

  18. Anomalous enthalpy relaxation in vitreous silica

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    2015-01-01

    scans. It is known that the liquid fragility (i.e., the speed of the viscous slow-down of a supercooled liquid at its Tg during cooling) has impact on enthalpy relaxation in glass. Here, we find that vitreous silica (as a strong system) exhibits striking anomalies in both glass transition and enthalpy...... relaxation compared to fragile oxide systems. The anomalous enthalpy relaxation of vitreous silica is discovered by performing the hyperquenching-annealing-calorimetry experiments. We argue that the strong systems like vitreous silica and vitreous Germania relax in a structurally cooperative manner, whereas...... the fragile ones do in a structurally independent fashion. We discuss the origin of the anomalous enthalpy relaxation in the HQ vitreous silica....

  19. Vibrational and Rotational Energy Relaxation in Liquids

    DEFF Research Database (Denmark)

    Petersen, Jakob

    Vibrational and rotational energy relaxation in liquids are studied by means of computer simulations. As a precursor for studying vibrational energy relaxation of a solute molecule subsequent to the formation of a chemical bond, the validity of the classical Bersohn-Zewail model for describing......, the vibrational energy relaxation of I2 subsequent to photodissociation and recombination in CCl4 is studied using classical Molecular Dynamics simulations. The vibrational relaxation times and the time-dependent I-I pair distribution function are compared to new experimental results, and a qualitative agreement...... is found in both cases. Furthermore, the rotational energy relaxation of H2O in liquid water is studied via simulations and a power-and-work analysis. The mechanism of the energy transfer from the rotationally excited H2O molecule to its water neighbors is elucidated, i.e. the energy-accepting degrees...

  20. Cross-relaxation solid state lasers

    International Nuclear Information System (INIS)

    Antipenko, B.M.

    1989-01-01

    Cross-relaxation functional diagrams provide a high quantum efficiency for pumping bands of solid state laser media and a low waste heat. A large number of the cross-relaxation mechanisms for decay rare earth excited states in crystals have been investigated. These investigations have been a starting-point for development of the cross-relaxation solid state lasers. For example, the cross-relaxation interactions, have been used for the laser action development of LiYF 4 :Gd-Tb. These interactions are important elements of the functional diagrams of the 2 μm Ho-doped media sensitized with Er and Tm and the 3 μm Er-doped media. Recently, new efficient 2 μm laser media with cross-relaxation pumping diagrams have been developed. Physical aspects of these media are the subject of this paper. A new concept of the Er-doped medium, sensitized with Yb, is illustrated

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Magnetic Resonance Fingerprinting with short relaxation intervals.

    Science.gov (United States)

    Amthor, Thomas; Doneva, Mariya; Koken, Peter; Sommer, Karsten; Meineke, Jakob; Börnert, Peter

    2017-09-01

    The aim of this study was to investigate a technique for improving the performance of Magnetic Resonance Fingerprinting (MRF) in repetitive sampling schemes, in particular for 3D MRF acquisition, by shortening relaxation intervals between MRF pulse train repetitions. A calculation method for MRF dictionaries adapted to short relaxation intervals and non-relaxed initial spin states is presented, based on the concept of stationary fingerprints. The method is applicable to many different k-space sampling schemes in 2D and 3D. For accuracy analysis, T 1 and T 2 values of a phantom are determined by single-slice Cartesian MRF for different relaxation intervals and are compared with quantitative reference measurements. The relevance of slice profile effects is also investigated in this case. To further illustrate the capabilities of the method, an application to in-vivo spiral 3D MRF measurements is demonstrated. The proposed computation method enables accurate parameter estimation even for the shortest relaxation intervals, as investigated for different sampling patterns in 2D and 3D. In 2D Cartesian measurements, we achieved a scan acceleration of more than a factor of two, while maintaining acceptable accuracy: The largest T 1 values of a sample set deviated from their reference values by 0.3% (longest relaxation interval) and 2.4% (shortest relaxation interval). The largest T 2 values showed systematic deviations of up to 10% for all relaxation intervals, which is discussed. The influence of slice profile effects for multislice acquisition is shown to become increasingly relevant for short relaxation intervals. In 3D spiral measurements, a scan time reduction of 36% was achieved, maintaining the quality of in-vivo T1 and T2 maps. Reducing the relaxation interval between MRF sequence repetitions using stationary fingerprint dictionaries is a feasible method to improve the scan efficiency of MRF sequences. The method enables fast implementations of 3D spatially

  10. Strengthening and stress relaxation of Opalinus Clay

    International Nuclear Information System (INIS)

    Schulze, Otto

    2010-01-01

    undisturbed far-field for the long lasting periods of geological times. Consequently, demands on concepts for backfilling and closure of a repository in a clay-stone formation as well as model calculations for safety analyses generally do not take into account convergence by viscous deformation, which would result from stress re-distribution at underground openings. Although there is some doubt, whether Opalinus Clay is creeping at all, some very long lasting laboratory tests were performed on this item in the author's laboratory. A nearly linear dependence of the long-term creep rate on the deviatoric stress was found. In recent work, the technique of stress-relaxation was used. For this, strengthening by strain rate controlled deformation was stopped, i.e. the strain was kept constant for a long time, and the relaxation of the stress was measured. In course of this technique, the deformability which may result from artefacts is ruled out as far as possible by compaction and strengthening. Then, the stress relaxation - if any - will be maintained by true long-term deformation processes which should be active and responsible for any convergence in an at least only partly backfilled mine. In this contribution, the results of the laboratory work and their discussion will be presented. (authors)

  11. Tracking ultrafast relaxation dynamics of furan by femtosecond photoelectron imaging

    International Nuclear Information System (INIS)

    Liu, Yuzhu; Knopp, Gregor; Qin, Chaochao; Gerber, Thomas

    2015-01-01

    Graphical abstract: - Highlights: • Relaxation dynamics of furan are tracked by femtosecond photoelectron imaging. • The mechanism for ultrafast formation of α-carbene and β-carbene is proposed. • Ultrafast internal conversion from S 2 to S 1 is observed. • The transient characteristics of the fragment ions are obtained. • Single-color multi-photon ionization dynamics at 800 nm are also studied. - Abstract: Ultrafast internal conversion dynamics of furan has been studied by femtosecond photoelectron imaging (PEI) coupled with photofragmentation (PF) spectroscopy. Photoelectron imaging of single-color multi-photon ionization and two-color pump–probe ionization are obtained and analyzed. Photoelectron bands are assigned to the related states. The time evolution of the photoelectron signal by pump–probe ionization can be well described by a biexponential decay: two rapid relaxation pathways with time constants of ∼15 fs and 85 (±11) fs. The rapid relaxation is ascribed to the ultrafast internal conversion (IC) from the S 2 state to the vibrationally hot S 1 state. The second relaxation process is attributed to the redistributions and depopulation of secondarily populated high vibronic S 1 state and the formation of α-carbene and β-carbene by H immigration. Additionally, the transient characteristics of the fragment ions are also measured and discussed as a complementary understanding

  12. Tracking ultrafast relaxation dynamics of furan by femtosecond photoelectron imaging

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yuzhu, E-mail: yuzhu.liu@gmail.com [School of Physics and Optoelectronic Engineering, Nanjing University of Information Science and Technology, Nanjing 210044 (China); Knopp, Gregor [Paul Scherrer Institute, Villigen 5232 (Switzerland); Qin, Chaochao [Department of Physics, Henan Normal University, Xinxiang 453007 (China); Gerber, Thomas [Paul Scherrer Institute, Villigen 5232 (Switzerland)

    2015-01-13

    Graphical abstract: - Highlights: • Relaxation dynamics of furan are tracked by femtosecond photoelectron imaging. • The mechanism for ultrafast formation of α-carbene and β-carbene is proposed. • Ultrafast internal conversion from S{sub 2} to S{sub 1} is observed. • The transient characteristics of the fragment ions are obtained. • Single-color multi-photon ionization dynamics at 800 nm are also studied. - Abstract: Ultrafast internal conversion dynamics of furan has been studied by femtosecond photoelectron imaging (PEI) coupled with photofragmentation (PF) spectroscopy. Photoelectron imaging of single-color multi-photon ionization and two-color pump–probe ionization are obtained and analyzed. Photoelectron bands are assigned to the related states. The time evolution of the photoelectron signal by pump–probe ionization can be well described by a biexponential decay: two rapid relaxation pathways with time constants of ∼15 fs and 85 (±11) fs. The rapid relaxation is ascribed to the ultrafast internal conversion (IC) from the S{sub 2} state to the vibrationally hot S{sub 1} state. The second relaxation process is attributed to the redistributions and depopulation of secondarily populated high vibronic S{sub 1} state and the formation of α-carbene and β-carbene by H immigration. Additionally, the transient characteristics of the fragment ions are also measured and discussed as a complementary understanding.

  13. Relaxation model of radiation-induced conductivity in polymers

    Science.gov (United States)

    Zhutayeva, Yu. R.; Khatipov, S. A.

    1999-05-01

    The paper suggests a relaxation model of radiation-induced conductivity (RIC) in polymers. According to the model, the transfer of charges generated in the polymer volume by ionizing radiation takes place with the participation of molecular relaxation processes. The mechanism of electron transport consists in the transfer of the charge directly between traps when they draw close to one another due to the rotation of macromolecule segments. The numerical solutions of the corresponding kinetic equations for different distribution functions Q( τ) of the times of molecular relaxation and for different functions of the probability P( τ, τ') of charge transfer in the `overlapping' regions of the diffusion spheres of the segments are analyzed. The relaxation model provides an explanation of the non-Arrhenius behavior of the RIC temperature dependence, the power dependence of RIC on the dose rate with a power index in the interval 0.5-1.0, the appearance of maxima in the curves of the RIC temporal dependence and their irreversible character in the region of large dose rates (more than 1 Gy/s). The model can be used for interpreting polymer RIC in conditions of kinetic mobility of macromolecules.

  14. Creep and stress relaxation behavior of two soft denture liners.

    Science.gov (United States)

    Salloum, Alaa'a M

    2014-03-01

    Numerous investigators stated the indications of soft denture lining materials; but no one determined the indications of these materials according to their chemical structure. The purpose of this investigation was to evaluate the viscoelastic properties of acrylic and silicon lining materials. This study investigated and compared viscoelastic properties of two resilient denture lining materials. Tested materials were laboratory processed; one of them was silicone-based liner product (Molloplast-B), and the other was plasticized acrylic resin (Vertex™ Soft). Twenty cylindrical specimens (10-20 mm in length, 11.55 mm in diameter) were fabricated in an aluminum mold from each material for creep and stress relaxation testing (the study of viscoelastic properties). Tests were performed by using the universal testing machine DY-34. Collected data were analyzed with t test statistics for statistically significant differences at the 95 % confidence level. There was a clear difference in creep and stress relaxation behavior between acrylic and silicone liners. Statistical study of Young's moduli illustrated that Vertex™ Soft was softer than Molloplast-B. On the other hand, the results explained that the recovery of silicone material was better than of acrylic one. The creep test revealed that the plasticized acrylic resin lining material exhibited considerable creep, whereas silicone-based liner exhibited elastic behavior. Besides, the stress relaxation test showed that relaxation of the plasticized acrylic resin material was bigger than of the silicone-based liner.

  15. Relaxing a large cosmological constant

    International Nuclear Information System (INIS)

    Bauer, Florian; Sola, Joan; Stefancic, Hrvoje

    2009-01-01

    The cosmological constant (CC) problem is the biggest enigma of theoretical physics ever. In recent times, it has been rephrased as the dark energy (DE) problem in order to encompass a wider spectrum of possibilities. It is, in any case, a polyhedric puzzle with many faces, including the cosmic coincidence problem, i.e. why the density of matter ρ m is presently so close to the CC density ρ Λ . However, the oldest, toughest and most intriguing face of this polyhedron is the big CC problem, namely why the measured value of ρ Λ at present is so small as compared to any typical density scale existing in high energy physics, especially taking into account the many phase transitions that our Universe has undergone since the early times, including inflation. In this Letter, we propose to extend the field equations of General Relativity by including a class of invariant terms that automatically relax the value of the CC irrespective of the initial size of the vacuum energy in the early epochs. We show that, at late times, the Universe enters an eternal de Sitter stage mimicking a tiny positive cosmological constant. Thus, these models could be able to solve the big CC problem without fine-tuning and have also a bearing on the cosmic coincidence problem. Remarkably, they mimic the ΛCDM model to a large extent, but they still leave some characteristic imprints that should be testable in the next generation of experiments.

  16. Relaxation in Thin Polymer Films Mapped across the Film Thickness by Astigmatic Single-Molecule Imaging

    KAUST Repository

    Oba, Tatsuya; Vacha, Martin

    2012-01-01

    We have studied relaxation processes in thin supported films of poly(methyl acrylate) at the temperature corresponding to 13 K above the glass transition by monitoring the reorientation of single perylenediimide molecules doped into the films

  17. The effects of progressive muscle relaxation and autogenic relaxation on young soccer players' mood states.

    Science.gov (United States)

    Hashim, Hairul Anuar; Hanafi Ahmad Yusof, Hazwani

    2011-06-01

    This study was designed to compare the effects of two different relaxation techniques, namely progressive muscle relaxation (PMR) and autogenic relaxation (AGR) on moods of young soccer players. sixteen adolescent athletes (mean age: 14.1 ± 1.3) received either PMR or AGR training. Using Profile of Mood States- Adolescents, their mood states were measured one week before relaxation training, before the first relaxation session, and after the twelfth relaxation session. Mixed ANOVA revealed no significant interaction effects and no significant main effects in any of the subscales. However, significant main effects for testing sessions were found for confusion, depression, fatigue, and tension subscales. Post hoc tests revealed post-intervention reductions in the confusion, depression, fatigue, and tension subscale scores. These two relaxation techniques induce equivalent mood responses and may be used to regulate young soccer players' mood states.

  18. The Effects of Progressive Muscle Relaxation and Autogenic Relaxation on Young Soccer Players’ Mood States

    Science.gov (United States)

    Hashim, Hairul Anuar; Hanafi@Ahmad Yusof, Hazwani

    2011-01-01

    Purpose This study was designed to compare the effects of two different relaxation techniques, namely progressive muscle relaxation (PMR) and autogenic relaxation (AGR) on moods of young soccer players. Methods Sixteen adolescent athletes (mean age: 14.1 ± 1.3) received either PMR or AGR training. Using Profile of Mood States- Adolescents, their mood states were measured one week before relaxation training, before the first relaxation session, and after the twelfth relaxation session. Results Mixed ANOVA revealed no significant interaction effects and no significant main effects in any of the subscales. However, significant main effects for testing sessions were found for confusion, depression, fatigue, and tension subscales. Post hoc tests revealed post-intervention reductions in the confusion, depression, fatigue, and tension subscale scores. Conclusion These two relaxation techniques induce equivalent mood responses and may be used to regulate young soccer players’ mood states. PMID:22375225

  19. Orientational order and rotational relaxation in the plastic crystal phase of tetrahedral molecules.

    Science.gov (United States)

    Rey, Rossend

    2008-01-17

    A methodology recently introduced to describe orientational order in liquid carbon tetrachloride is extended to the plastic crystal phase of XY4 molecules. The notion that liquid and plastic crystal phases are germane regarding orientational order is confirmed for short intermolecular distances but is seen to fail beyond, as long range orientational correlations are found for the simulated solid phase. It is argued that, if real, such a phenomenon may not to be accessible with direct (diffraction) methods due to the high molecular symmetry. This behavior is linked to the existence of preferential orientation with respect to the fcc crystalline network defined by the centers of mass. It is found that the dominant class accounts, at most, for one-third of all configurations, with a feeble dependence on temperature. Finally, the issue of rotational relaxation is also addressed, with an excellent agreement with experimental measures. It is shown that relaxation is nonhomogeneous in the picosecond range, with a slight dispersion of decay times depending on the initial orientational class. The results reported mainly correspond to neopentane over a wide temperature range, although results for carbon tetrachloride are included, as well.

  20. 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.

  1. Novel spin dynamics in ferrimagnetic molecular chains from {sup 1}H NMR and {mu}SR spin-lattice relaxation measurements

    Energy Technology Data Exchange (ETDEWEB)

    Micotti, E. E-mail: micotti@fisicavolta.unipv.it; Lascialfari, A.; Rigamonti, A.; Aldrovandi, S.; Caneschi, A.; Gatteschi, D.; Bogani, L

    2004-05-01

    The spin dynamics in the helical chain Co(hfac){sub 2}NITPhOMe has been investigated by {sup 1}H NMR and {mu}SR relaxation. In the temperature range 15relaxation of the homogeneous magnetization. For T{<=}15 K, NMR and {mu}SR evidence a second spin relaxation mechanism, undetected by the magnetization measurements. From the analysis of these data, insights on this novel relaxation process are derived.

  2. Image Relaxation Matching Based on Feature Points for DSM Generation

    Institute of Scientific and Technical Information of China (English)

    ZHENG Shunyi; ZHANG Zuxun; ZHANG Jianqing

    2004-01-01

    In photogrammetry and remote sensing, image matching is a basic and crucial process for automatic DEM generation. In this paper we presented a image relaxation matching method based on feature points. This method can be considered as an extention of regular grid point based matching. It avoids the shortcome of grid point based matching. For example, with this method, we can avoid low or even no texture area where errors frequently appear in cross correlaton matching. In the mean while, it makes full use of some mature techniques such as probability relaxation, image pyramid and the like which have already been successfully used in grid point matching process. Application of the technique to DEM generaton in different regions proved that it is more reasonable and reliable.

  3. Relaxation labelling-the principle of least disturbance

    Energy Technology Data Exchange (ETDEWEB)

    Blake, A

    1983-07-01

    Relaxation labelling may be an important method of programming parallel array processors. Work on image recognition systems makes it clear that extraction of primitive descriptions of objects from image data is a processing bottleneck. Badly needed processing power could be obtained from special hardware but the parallel array processor is a flexible source of power because it is programmable, and should become cheaper as it continues to be developed. Parallel array processors perform local operations like convolution and thresholding very efficiently. However, extraction of lines and curves, as primitives for object description, involve operations which are not local, because the edges are long and must be examined over their entire length. Relaxation labelling achieves a global effect by repeated application of a local operation. The way of deriving that local operation from a problem specification, and the relationship to constrained optimisation, is the subject of the paper. 18 references.

  4. Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: longitudinal relaxation dispersion for a dipole-coupled spin-1/2 pair.

    Science.gov (United States)

    Chang, Zhiwei; Halle, Bertil

    2013-10-14

    In complex biological or colloidal samples, magnetic relaxation dispersion (MRD) experiments using the field-cycling technique can characterize molecular motions on time scales ranging from nanoseconds to microseconds, provided that a rigorous theory of nuclear spin relaxation is available. In gels, cross-linked proteins, and biological tissues, where an immobilized macromolecular component coexists with a mobile solvent phase, nuclear spins residing in solvent (or cosolvent) species relax predominantly via exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings. The physical or chemical exchange processes that dominate the MRD typically occur on a time scale of microseconds or longer, where the conventional perturbation theory of spin relaxation breaks down. There is thus a need for a more general relaxation theory. Such a theory, based on the stochastic Liouville equation (SLE) for the EMOR mechanism, is available for a single quadrupolar spin I = 1. Here, we present the corresponding theory for a dipole-coupled spin-1/2 pair. To our knowledge, this is the first treatment of dipolar MRD outside the motional-narrowing regime. Based on an analytical solution of the spatial part of the SLE, we show how the integral longitudinal relaxation rate can be computed efficiently. Both like and unlike spins, with selective or non-selective excitation, are treated. For the experimentally important dilute regime, where only a small fraction of the spin pairs are immobilized, we obtain simple analytical expressions for the auto-relaxation and cross-relaxation rates which generalize the well-known Solomon equations. These generalized results will be useful in biophysical studies, e.g., of intermittent protein dynamics. In addition, they represent a first step towards a rigorous theory of water (1)H relaxation in biological tissues, which is a prerequisite for unravelling the molecular basis of soft

  5. Relaxation of polarized nuclei in superconducting rhodium

    DEFF Research Database (Denmark)

    Knuuttila, T.A.; Tuoriniemi, J.T.; Lefmann, K.

    2000-01-01

    Nuclear spin lattice relaxation rates were measured in normal and superconducting (sc) rhodium with nuclear polarizations up to p = 0.55. This was sufficient to influence the sc state of Rh, whose T, and B-c, are exceptionally low. Because B-c ... is unchanged, the nuclear spin entropy was fully sustained across the sc transition. The relaxation in the sc state was slower at all temperatures without the coherence enhancement close to T-c. Nonzero nuclear polarization strongly reduced the difference between the relaxation rates in the sc and normal...

  6. Spin relaxation in nanowires by hyperfine coupling

    International Nuclear Information System (INIS)

    Echeverria-Arrondo, C.; Sherman, E.Ya.

    2012-01-01

    Hyperfine interactions establish limits on spin dynamics and relaxation rates in ensembles of semiconductor quantum dots. It is the confinement of electrons which determines nonzero hyperfine coupling and leads to the spin relaxation. As a result, in nanowires one would expect the vanishing of this effect due to extended electron states. However, even for relatively clean wires, disorder plays a crucial role and makes electron localization sufficient to cause spin relaxation on the time scale of the order of 10 ns. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  7. Le Chatelier's principle with multiple relaxation channels

    Science.gov (United States)

    Gilmore, R.; Levine, R. D.

    1986-05-01

    Le Chatelier's principle is discussed within the constrained variational approach to thermodynamics. The formulation is general enough to encompass systems not in thermal (or chemical) equilibrium. Particular attention is given to systems with multiple constraints which can be relaxed. The moderation of the initial perturbation increases as additional constraints are removed. This result is studied in particular when the (coupled) relaxation channels have widely different time scales. A series of inequalities is derived which describes the successive moderation as each successive relaxation channel opens up. These inequalities are interpreted within the metric-geometry representation of thermodynamics.

  8. Universal Mechanism of Spin Relaxation in Solids

    Science.gov (United States)

    Chudnovsky, Eugene

    2006-03-01

    Conventional elastic theory ignores internal local twists and torques. Meantime, spin-lattice relaxation is inherently coupled with local elastic twists through conservation of the total angular momentum (spin + lattice). This coupling gives universal lower bound (free of fitting parameters) on the relaxation of the atomic or molecular spin in a solid [1] and on the relaxation of the electron spin in a quantum dot [2]. [1] E. M. Chudnovsky, D. A. Garanin, and R. Schilling, Phys. Rev. B 72, 094426 (2005). [2] C. Calero, E. M. Chudnovsky, and D. A. Garanin, Phys. Rev. Lett. 95, 166603 (2005).

  9. Collisional relaxation of electron tail distribution

    International Nuclear Information System (INIS)

    Yamagiwa, Mitsuru; Okamoto, Masao.

    1985-05-01

    Relaxation due to the Coulomb collisions of the electron velocity distribution function with a high energy tail is investigated in detail. In the course of the relaxation, a 'saddle' point can be created in velocity space owing to upsilon -3 dependence of the deflection rate and a positive slope or a 'dip' appears in the tail direction. The time evolution of the electron tail is studied analytically. A comparison is made with numerical results by using a Fokker-Planck code. Also discussed is the kinetic instability concerned with the positive slope during the relaxation. (author)

  10. Stress Relaxation in Entangled Polymer Melts

    DEFF Research Database (Denmark)

    Hou, Ji-Xuan; Svaneborg, Carsten; Everaers, Ralf

    2010-01-01

    We present an extensive set of simulation results for the stress relaxation in equilibrium and step-strained bead-spring polymer melts. The data allow us to explore the chain dynamics and the shear relaxation modulus, G(t), into the plateau regime for chains with Z=40 entanglements...... and into the terminal relaxation regime for Z=10. Using the known (Rouse) mobility of unentangled chains and the melt entanglement length determined via the primitive path analysis of the microscopic topological state of our systems, we have performed parameter-free tests of several different tube models. We find...

  11. Slow relaxation in weakly open rational polygons.

    Science.gov (United States)

    Kokshenev, Valery B; Vicentini, Eduardo

    2003-07-01

    The interplay between the regular (piecewise-linear) and irregular (vertex-angle) boundary effects in nonintegrable rational polygonal billiards (of m equal sides) is discussed. Decay dynamics in polygons (of perimeter P(m) and small opening Delta) is analyzed through the late-time survival probability S(m) approximately equal t(-delta). Two distinct slow relaxation channels are established. The primary universal channel exhibits relaxation of regular sliding orbits, with delta=1. The secondary channel is given by delta>1 and becomes open when m>P(m)/Delta. It originates from vertex order-disorder dual effects and is due to relaxation of chaoticlike excitations.

  12. [A study on Korean concepts of relaxation].

    Science.gov (United States)

    Park, J S

    1992-01-01

    Relaxation technique is an independent nursing intervention used in various stressful situations. The concept of relaxation must be explored for the meaning given by the people in their traditional thought and philosophy. Korean relaxation technique, wanting to become culturally acceptable and effective, is learning to recognize and develop Korean concepts, experiences, and musics of relaxation. This study was aimed at discovering Korean concepts, experiences and musics of relaxation and contributing the development of the relaxation technique for Korean people. The subjects were 59 nursing students, 39 hospitalized patients, 61 housewives, 21 rural residents and 16 researchers. Data were collected from September 4th to October 24th, 1991 by interviews or questionnaires. The data analysis was done by qualitative research method, and validity assured by conformation of the concept and category by 2 nursing scientists who had written a Master's thesis on the relaxation technique. The results of the study were summarized as follows; 1. The meaning of the relaxation concept; From 298 statements, 107 concepts were extracted and then 5 categories "Physical domain", "Psychological domain", "Complex domain", "Situation", and "environment" were organized. 'Don't have discomforts, 'don't have muscle tension', 'don't have energy (him in Korean)', 'don't have activities' subcategories were included in "Physical domain". 'Don't have anxiety', 'feel good', 'emotional stability', 'don't have wordly thoughts', 'feel one's brain muddled', 'loss of desire' subcategories were included in "physical domain" 'Comfort body and mind', 'don't have tension of body and mind', 'be sagged' 'liveliness of thoughts' subcategories were included in "Complex domain". 'Rest', 'sleep', 'others' subcategories were included in "Situation domain". And 'quite environment' & 'comfortable environment' subcategories were included in "Environmental domain". 2. The experiences of the relaxation; From 151

  13. Stretched exponential relaxation in molecular and electronic glasses

    Science.gov (United States)

    Phillips, J. C.

    1996-09-01

    Stretched exponential relaxation, 0034-4885/59/9/003/img1, fits many relaxation processes in disordered and quenched electronic and molecular systems, but it is widely believed that this function has no microscopic basis, especially in the case of molecular relaxation. For electronic relaxation the appearance of the stretched exponential is often described in the context of dispersive transport, where 0034-4885/59/9/003/img2 is treated as an adjustable parameter, but in almost all cases it is generally assumed that no microscopic meaning can be assigned to 0034-4885/59/9/003/img3 even at 0034-4885/59/9/003/img4, a glass transition temperature. We show that for molecular relaxation 0034-4885/59/9/003/img5 can be understood, providing that one separates extrinsic and intrinsic effects, and that the intrinsic effects are dominated by two magic numbers, 0034-4885/59/9/003/img6 for short-range forces, and 0034-4885/59/9/003/img7 for long-range Coulomb forces, as originally observed by Kohlrausch for the decay of residual charge on a Leyden jar. Our mathematical model treats relaxation kinetics using the Lifshitz - Kac - Luttinger diffusion to traps depletion model in a configuration space of effective dimensionality, the latter being determined using axiomatic set theory and Phillips - Thorpe constraint theory. The experiments discussed include ns neutron scattering experiments, particularly those based on neutron spin echoes which measure S( Q,t) directly, and the traditional linear response measurements which span the range from 0034-4885/59/9/003/img8 to s, as collected and analysed phenomenologically by Angell, Ngai, Böhmer and others. The electronic materials discussed include a-Si:H, granular 0034-4885/59/9/003/img9, semiconductor nanocrystallites, charge density waves in 0034-4885/59/9/003/img10, spin glasses, and vortex glasses in high-temperature semiconductors. The molecular materials discussed include polymers, network glasses, electrolytes and alcohols, Van

  14. Stretched exponential relaxation in molecular and electronic glasses

    International Nuclear Information System (INIS)

    Phillips, J.C.

    1996-01-01

    Stretched exponential relaxation, exp[-(t/τ) β ], fits many relaxation processes in disordered and quenched electronic and molecular systems, but it is widely believed that this function has no microscopic basis, especially in the case of molecular relaxation. For electronic relaxation the appearance of the stretched exponential is often described in the context of dispersive transport, where β is treated as an adjustable parameter, but in almost all cases it is generally assumed that no microscopic meaning can be assigned to 0 g , a glass transition temperature. We show that for molecular relaxation β(T g ) can be understood, providing that one separates extrinsic and intrinsic effects, and that the intrinsic effects are dominated by two magic numbers, β SR =3/5 for short-range forces, and β K =3/7 for long-range Coulomb forces, as originally observed by Kohlrausch for the decay of residual charge on a Leyden jar. Our mathematical model treats relaxation kinetics using the Lifshitz-Kac-Luttinger diffusion to traps depletion model in a configuration space of effective dimensionality, the latter being determined using axiomatic set theory and Phillips-Thorpe constraint theory. The experiments discussed include ns neutron scattering experiments, particularly those based on neutron spin echoes which measure S(Q, t) directly, and the traditional linear response measurements which span the range from μs to s, as collected and analysed phenomenologically by Angell, Ngai, Boehmer and others. The electronic materials discussed include a-Si:H, granular C 60 , semiconductor nanocrystallites, charge density waves in TaS 3 , spin glasses, and vortex glasses in high-temperature semiconductors. The molecular materials discussed include polymers, network glasses, electrolytes and alcohols, Van der Waals supercooled liquids and glasses, orientational glasses, water, fused salts, and heme proteins. In the intrinsic cases the theory of β(T g ) is often accurate to 2%, which

  15. F-center mechanism of long-term relaxation in lead zirconate-titanate-based piezoelectric ceramics. 1. After-heating relaxation

    Directory of Open Access Journals (Sweden)

    V. M. Ishchuk

    2015-12-01

    The oxygen vacancies-based model for description of the long-time relaxation processes is suggested. The model takes into account oxygen vacancies on the sample’s surface ends, their conversion into F+- and F0-centers under external effects (due to the liberation of the pyroelectric charge and subsequent relaxation of these centers into the simple oxygen vacancies after the actions termination. The initial sample’s state is electroneutrality one. F-center formation leads to the violation of the original sample’s electroneutrality, and generates DC electric field into the sample. Relaxation of F-centers is accompanied by decreasing of electric field, induced by them, and dielectric constant relaxation as consequent effect.

  16. Nonequilibrium thermodynamics and information theory: basic concepts and relaxing dynamics

    Science.gov (United States)

    Altaner, Bernhard

    2017-11-01

    Thermodynamics is based on the notions of energy and entropy. While energy is the elementary quantity governing physical dynamics, entropy is the fundamental concept in information theory. In this work, starting from first principles, we give a detailed didactic account on the relations between energy and entropy and thus physics and information theory. We show that thermodynamic process inequalities, like the second law, are equivalent to the requirement that an effective description for physical dynamics is strongly relaxing. From the perspective of information theory, strongly relaxing dynamics govern the irreversible convergence of a statistical ensemble towards the maximally non-commital probability distribution that is compatible with thermodynamic equilibrium parameters. In particular, Markov processes that converge to a thermodynamic equilibrium state are strongly relaxing. Our framework generalizes previous results to arbitrary open and driven systems, yielding novel thermodynamic bounds for idealized and real processes. , which features invited work from the best early-career researchers working within the scope of J. Phys. A. This project is part of the Journal of Physics series’ 50th anniversary celebrations in 2017. Bernhard Altaner was selected by the Editorial Board of J. Phys. A as an Emerging Talent.

  17. Universal properties of relaxation and diffusion in condensed matter

    International Nuclear Information System (INIS)

    Ngai K L

    2017-01-01

    By and large the research communities today are not fully aware of the remarkable universality in the dynamic properties of many-body relaxation/diffusion processes manifested in experiments and simulations on condensed matter with diverse chemical compositions and physical structures. I shall demonstrate the universality first from the dynamic processes in glass-forming systems. This is reinforced by strikingly similar properties of different processes in contrasting interacting systems all having nothing to do with glass transition. The examples given here include glass-forming systems of diverse chemical compositions and physical structures, conductivity relaxation of ionic conductors (liquid, glassy, and crystalline), translation and orientation ordered phase of rigid molecule, and polymer chain dynamics. Universality is also found in the change of dynamics when dimension is reduced to nanometer size in widely different systems. The remarkable universality indicates that many-body relaxation/diffusion is governed by fundamental physics to be unveiled. One candidate is classical chaos on which the coupling model is based, Universal properties predicted by this model are in accord with diverse experiments and simulations. (paper)

  18. Cross Relaxation in rare-earth-doped oxyfluoride glasses

    Energy Technology Data Exchange (ETDEWEB)

    Lakshminarayana, G.; Weis, Eric M. [Materials Science and Technology Division (MST-7), Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Lira, A.C. [Unidad Académica Profesional Nezahualcóyotl, Universidad Autónoma del Estado de México, Av. Bordo de Xochiaca s/n, Nezahualcóyotl, Estado de Mexico 57000, México (Mexico); Caldiño, Ulises [Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa, P.O. Box 55-534, México D.F. 09340 (Mexico); Williams, Darrick J. [Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Hehlen, Markus P., E-mail: hehlen@lanl.gov [Materials Science and Technology Division (MST-7), Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2013-07-15

    The excited-state relaxation dynamics of Tb{sup 3+}, Sm{sup 3+}, and Eu{sup 3+} doped into a 50SiO{sub 2}–20Al{sub 2}O{sub 3}–10Na{sub 2}O–20LaF{sub 3} (mol%) oxyfluoride glass are studied. Multiphonon relaxation of the primary emitting states in Tb{sup 3+} ({sup 5}D{sub 3} and {sup 5}D{sub 4}), Sm{sup 3+} ({sup 4}G{sub 5/2}), and Eu{sup 3+} ({sup 5}D{sub 0}) was found to be negligible in the present host. The relaxation of Tb{sup 3+} ({sup 5}D{sub 4}) and Eu{sup 3+} ({sup 5}D{sub 0}) is dominated by radiative decay. For Tb{sup 3+} ({sup 5}D{sub 3}) and Sm{sup 3+} ({sup 4}G{sub 5/2}) in contrast, radiative relaxation is in competition with several non-radiative cross-relaxation processes. This competition was found to be particularly pronounced for the {sup 5}D{sub 3} excited state in Tb{sup 3+}, where a 124-fold decrease of the ({sup 5}D{sub 3}→{sup 7}F{sub 5})/({sup 5}D{sub 4}→{sup 7}F{sub 5}) emission intensity ratio and a ∼10-fold shortening of the {sup 5}D{sub 3} lifetime was observed upon increasing the Tb{sup 3+} concentration from 0.01% to 1%. The Tb{sup 3+} concentration dependence of {sup 5}D{sub 3} also points to some degree of ion aggregation in the “as quenched” glasses. A Judd–Ofelt intensity analysis was performed for Sm{sup 3+} and used to estimate the relative magnitude of {sup 4}G{sub 5/2} cross-relaxation processes. Four cross-relaxation processes in particular were identified to account for 92% of the total {sup 4}G{sub 5/2} non-radiative decay, and a 11% quantum efficiency was estimated for the {sup 4}G{sub 5/2} excited state. Non-exponentiality in the {sup 5}D{sub 0} decay of Eu{sup 3+} is evidence for several Eu{sup 3+} coordination environments in the glass host that manifest in different {sup 5}D{sub 0} decay constants because of the hypersensitivity of the {sup 5}D{sub 0}→{sup 7}F{sub 2} transition. -- Highlights: ► Tb{sup 3+}, Sm{sup 3+}, and Eu{sup 3+} were doped into a LaF{sub 3}-rich oxyfluoride glass. ► The

  19. 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

  20. 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.

  1. 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...

  2. 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)

  3. 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.

  4. 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.

  5. 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...

  6. 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

  7. 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 ...

  8. 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.

  9. 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

  10. Study on Relaxation Damage Properties of High Viscosity Asphalt Sand under Uniaxial Compression

    Directory of Open Access Journals (Sweden)

    Yazhen Sun

    2018-01-01

    Full Text Available Laboratory investigations of relaxation damage properties of high viscosity asphalt sand (HVAS by uniaxial compression tests and modified generalized Maxwell model (GMM to simulate viscoelastic characteristics coupling damage were carried out. A series of uniaxial compression relaxation tests were performed on HVAS specimens at different temperatures, loading rates, and constant levels of input strain. The results of the tests show that the peak point of relaxation modulus is highly influenced by the loading rate in the first half of an L-shaped curve, while the relaxation modulus is almost constant in the second half of the curve. It is suggested that for the HVAS relaxation tests, the temperature should be no less than −15°C. The GMM is used to determine the viscoelastic responses, the Weibull distribution function is used to characterize the damage of the HVAS and its evolution, and the modified GMM is a coupling of the two models. In this paper, the modified GMM is implemented through a secondary development with the USDFLD subroutine to analyze the relaxation damage process and improve the linear viscoelastic model in ABAQUS. Results show that the numerical method of coupling damage provides a better approximation of the test curve over almost the whole range. The results also show that the USDFLD subroutine can effectively predict the relaxation damage process of HVAS and can provide a theoretical support for crack control of asphalt pavements.

  11. The relaxation of plasmas with dust particles

    International Nuclear Information System (INIS)

    Chutov, Yu.I.; Kravchenko, A.Yu.; Schram, P.P.J.M.

    1997-01-01

    Various parameters of relaxing plasmas with dust particles including the electron and ion energy distributions function are numerically simulated at various parameters of the dust particles using the PIC method and taking into account the dynamics of the dust particle charge without the assumption about the equilibrium of electrons and ions. Coulomb collisions are taken into account in the framework of the method of stochastic differential equations. The relaxation of bounded plasma clouds expanding into a vacuum as well as the relaxation of a uniform plasma, in which dust particles appear at some initial time, are investigated. The obtained results show that the relaxation of plasmas can be accompanied by a deviation of the ion distribution function from equilibrium as well as a change of the mean energy of electrons and ions because of the dependence of the collection of electrons and ions by dust particles on their energy. (author)

  12. Multiscale dipole relaxation in dielectric materials

    DEFF Research Database (Denmark)

    Hansen, Jesper Schmidt

    2016-01-01

    Dipole relaxation from thermally induced perturbations is investigated on different length scales for dielectric materials. From the continuum dynamical equations for the polarisation, expressions for the transverse and longitudinal dipole autocorrelation functions are derived in the limit where ...

  13. Generalized approach to non-exponential relaxation

    Indian Academy of Sciences (India)

    Non-exponential relaxation is a universal feature of systems as diverse as glasses, spin ... which changes from a simple exponential to a stretched exponential and a power law by increasing the constraints in the system. ... Current Issue

  14. Oxygen-17 relaxation in aqueous agarose gels

    International Nuclear Information System (INIS)

    Ablett, S.; Lillford, P.J.

    1977-01-01

    Nuclear magnetic relaxation of oxygen-17 in H 2 17 O enriched agarose gels shows that existing explanations of water behaviour are oversimplified. Satisfactory models must include at least three proton phases, two of which involve water molecules. (Auth.)

  15. Relaxation study of a paramagnetic ion by the observation of nuclear resonance signals

    International Nuclear Information System (INIS)

    Landesman, A.

    1960-01-01

    Dynamic polarization of protons in water containing the paramagnetic ion NO(SO 3 ) 2 was studied, both theoretically and experimentally, as a function of magnetic field. The enhancement of the proton polarization depends appreciably on the relaxation process of the electron spin and so enables us to decide which is the real relaxation process. We tried the two following processes: a) The electron spin is coupled with the nitrogen magnetic moment by hyperfine interaction; if this interaction has an anisotropic part, a relaxation process for the electronic spin will result through the Brownian motion of the ion. b) The relaxation of the electron spin takes place through spin-orbit coupling of the electron spin. Experimental results showed that the relaxation took place through the second process with the help of dynamic polarization we were able to study the relaxation of an electron spin in a liquid without using any electron resonance spectrometer, simply by observing the resonance of a nuclear spin coupled with the electron spin. Reprint of a paper published in Le Journal de Physique et le Radium, t. 20, p. 937-948, 1959 [fr

  16. 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

  17. 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

  18. 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

  19. 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.

  20. Investigation of dielectric relaxation in systems with hierarchical organization: From time to frequency domain and back again

    Energy Technology Data Exchange (ETDEWEB)

    Yokoi, Koki [Department of Physics, University of Wisconsin-Milwaukee, Milwaukee, WI (United States); Raicu, Valerică, E-mail: vraicu@uwm.edu [Department of Physics, University of Wisconsin-Milwaukee, Milwaukee, WI (United States); Department of Biological Sciences, University of Wisconsin-Milwaukee, Milwaukee, WI (United States)

    2017-06-28

    Relaxation in fractal structures was investigated theoretically starting from a simple model of a Cantorian tree and kinetic equations linking the change in the number of particles (e.g., electrical charges) populating each branch of the tree and their transfer to other branches or to the ground state. We numerically solved the system of differential equations obtained and determined the so-called cumulative distribution function of particles, which, in dielectric or mechanical relaxation parlance, is the same as the relaxation function of the system. As a physical application, we studied the relationship between the dielectric relaxation in time-domain and the dielectric dispersion in the frequency-domain. Upon choosing appropriate rate constants, our model described accurately well-known non-exponential and non-Debye time- and frequency-domain functions, such as stretched exponentials, Havrilliak–Negami, and frequency power law. Our approach opens the door to applying kinetic models to describe a wide array of relaxation processes, which traditionally have posed great challenges to theoretical modeling based on first principles. - Highlights: • Relaxation was investigated for a system of particles flowing through a Cantorian tree. • A set of kinetic equations was formulated and used to compute the relaxation function of the system. • The dispersion function of the system was computed from the relaxation function. • An analytical method was used to recover the original relaxation function from the dispersion function. • This formalism was used to study dielectric relaxation and dispersion in fractal structures.

  1. Ghost lines in Moessbauer relaxation spectra

    International Nuclear Information System (INIS)

    Price, D.C.

    1985-01-01

    The appearance in Moessbauer relaxation spectra of 'ghost' lines, which are narrow lines that do not correspond to transitions between real hyperfine energy levels of the resonant system, is examined. It is shown that in many cases of interest, the appearance of these 'ghost' lines can be interpreted in terms of the relaxational averaging of one or more of the static interactions of the ion. (orig.)

  2. Dynamics of helicity transport and Taylor relaxation

    International Nuclear Information System (INIS)

    Diamond, P.H.; Malkov, M.

    2003-01-01

    A simple model of the dynamics of Taylor relaxation is derived using symmetry principles alone. No statistical closure approximations are invoked or detailed plasma model properties assumed. Notably, the model predicts several classes of nondiffusive helicity transport phenomena, including traveling nonlinear waves and superdiffusive turbulent pulses. A universal expression for the scaling of the effective magnetic Reynolds number of a system undergoing Taylor relaxation is derived. Some basic properties of intermittency in helicity transport are examined

  3. Turbulent Magnetic Relaxation in Pulsar Wind Nebulae

    Energy Technology Data Exchange (ETDEWEB)

    Zrake, Jonathan [Kavli Institute for Particle Astrophysics and Cosmology, Stanford University, SLAC National Accelerator Laboratory, Menlo Park, CA 94025 (United States); Arons, Jonathan [Astronomy Department and Theoretical Astrophysics Center, University of California, Berkeley, 601 Campbell Hall, Berkeley, CA 94720 (United States)

    2017-09-20

    We present a model for magnetic energy dissipation in a pulsar wind nebula. A better understanding of this process is required to assess the likelihood that certain astrophysical transients may be powered by the spin-down of a “millisecond magnetar.” Examples include superluminous supernovae, gamma-ray bursts, and anticipated electromagnetic counterparts to gravitational wave detections of binary neutron star coalescence. Our model leverages recent progress in the theory of turbulent magnetic relaxation to specify a dissipative closure of the stationary magnetohydrodynamic (MHD) wind equations, yielding predictions of the magnetic energy dissipation rate throughout the nebula. Synchrotron losses are self-consistently treated. To demonstrate the model’s efficacy, we show that it can reproduce many features of the Crab Nebula, including its expansion speed, radiative efficiency, peak photon energy, and mean magnetic field strength. Unlike ideal MHD models of the Crab (which lead to the so-called σ -problem), our model accounts for the transition from ultra to weakly magnetized plasma flow and for the associated heating of relativistic electrons. We discuss how the predicted heating rates may be utilized to improve upon models of particle transport and acceleration in pulsar wind nebulae. We also discuss implications for the Crab Nebula’s γ -ray flares, and point out potential modifications to models of astrophysical transients invoking the spin-down of a millisecond magnetar.

  4. Turbulent Magnetic Relaxation in Pulsar Wind Nebulae

    Science.gov (United States)

    Zrake, Jonathan; Arons, Jonathan

    2017-09-01

    We present a model for magnetic energy dissipation in a pulsar wind nebula. A better understanding of this process is required to assess the likelihood that certain astrophysical transients may be powered by the spin-down of a “millisecond magnetar.” Examples include superluminous supernovae, gamma-ray bursts, and anticipated electromagnetic counterparts to gravitational wave detections of binary neutron star coalescence. Our model leverages recent progress in the theory of turbulent magnetic relaxation to specify a dissipative closure of the stationary magnetohydrodynamic (MHD) wind equations, yielding predictions of the magnetic energy dissipation rate throughout the nebula. Synchrotron losses are self-consistently treated. To demonstrate the model’s efficacy, we show that it can reproduce many features of the Crab Nebula, including its expansion speed, radiative efficiency, peak photon energy, and mean magnetic field strength. Unlike ideal MHD models of the Crab (which lead to the so-called σ-problem), our model accounts for the transition from ultra to weakly magnetized plasma flow and for the associated heating of relativistic electrons. We discuss how the predicted heating rates may be utilized to improve upon models of particle transport and acceleration in pulsar wind nebulae. We also discuss implications for the Crab Nebula’s γ-ray flares, and point out potential modifications to models of astrophysical transients invoking the spin-down of a millisecond magnetar.

  5. Precession mechanism of spin relaxation at frequent electron-electron collisions

    CERN Document Server

    Glazov, M M

    2002-01-01

    It is shown that the spin relaxation mechanism in the two-dimensional electron gas, is controlled not only through the electron pulse relaxation processes, determining the mobility, but through the electron-electron collisions as well. It is decided to use the kinetic equation, describing the electron spin mixing in the k-space, for determining the spin relaxation time tau sub s at frequent electron-electron collisions. The tau sub s time is calculated for the nondegenerated electron gas both with an account and with no account of the exchange interaction

  6. Nuclear relaxation study of the spin dynamics in a one-dimensional Heisenberg system, TMMC

    International Nuclear Information System (INIS)

    Bakheit, M.A.

    1974-01-01

    Changes in the nuclear relaxation time as a function of the magnetic field intensity in TMMC are very different wether the field direction is parallel or perpendicular to the direction of the exchange chains (vector c). In parallel field, the relaxation probability increases as the field decreases. The process of spin diffusion in a one-dimensional system is well illustrated by the changes experimentally observed. In perpendicular field, the relaxation probability is constant as far as H 0 >2kG, it clearly decreases for H 0 [fr

  7. Stretched-exponential decay functions from a self-consistent model of dielectric relaxation

    International Nuclear Information System (INIS)

    Milovanov, A.V.; Rasmussen, J.J.; Rypdal, K.

    2008-01-01

    There are many materials whose dielectric properties are described by a stretched exponential, the so-called Kohlrausch-Williams-Watts (KWW) relaxation function. Its physical origin and statistical-mechanical foundation have been a matter of debate in the literature. In this Letter we suggest a model of dielectric relaxation, which naturally leads to a stretched exponential decay function. Some essential characteristics of the underlying charge conduction mechanisms are considered. A kinetic description of the relaxation and charge transport processes is proposed in terms of equations with time-fractional derivatives

  8. Relaxation of synchronization on complex networks.

    Science.gov (United States)

    Son, Seung-Woo; Jeong, Hawoong; Hong, Hyunsuk

    2008-07-01

    We study collective synchronization in a large number of coupled oscillators on various complex networks. In particular, we focus on the relaxation dynamics of the synchronization, which is important from the viewpoint of information transfer or the dynamics of system recovery from a perturbation. We measure the relaxation time tau that is required to establish global synchronization by varying the structural properties of the networks. It is found that the relaxation time in a strong-coupling regime (K>Kc) logarithmically increases with network size N , which is attributed to the initial random phase fluctuation given by O(N-1/2) . After elimination of the initial-phase fluctuation, the relaxation time is found to be independent of the system size; this implies that the local interaction that depends on the structural connectivity is irrelevant in the relaxation dynamics of the synchronization in the strong-coupling regime. The relaxation dynamics is analytically derived in a form independent of the system size, and it exhibits good consistency with numerical simulations. As an application, we also explore the recovery dynamics of the oscillators when perturbations enter the system.

  9. Stress relaxation in viscous soft spheres.

    Science.gov (United States)

    Boschan, Julia; Vasudevan, Siddarth A; Boukany, Pouyan E; Somfai, Ellák; Tighe, Brian P

    2017-10-04

    We report the results of molecular dynamics simulations of stress relaxation tests in athermal viscous soft sphere packings close to their unjamming transition. By systematically and simultaneously varying both the amplitude of the applied strain step and the pressure of the initial condition, we access both linear and nonlinear response regimes and control the distance to jamming. Stress relaxation in viscoelastic solids is characterized by a relaxation time τ* that separates short time scales, where viscous loss is substantial, from long time scales, where elastic storage dominates and the response is essentially quasistatic. We identify two distinct plateaus in the strain dependence of the relaxation time, one each in the linear and nonlinear regimes. The height of both plateaus scales as an inverse power law with the distance to jamming. By probing the time evolution of particle velocities during relaxation, we further identify a correlation between mechanical relaxation in the bulk and the degree of non-affinity in the particle velocities on the micro scale.

  10. Anisotropic intermolecular interaction and rotational ordering in hydrogen-containing solids. Progress report No. 12

    Energy Technology Data Exchange (ETDEWEB)

    1976-01-01

    Progress is reviewed in these areas: nuclear spin-lattice relaxation in ortho-para mixtures of solid deuterium below T/sub lambda/; pulsed NMR experiments of matrix isolated HCl; stimulated Raman scattering in solid hydrogen and nitrogen; and infrared line broadening of matrix isolated molecules. (GHT)

  11. Anisotropic intermolecular interaction and rotational ordering in hydrogen-containing solids. Progress report No. 12

    International Nuclear Information System (INIS)

    1976-01-01

    Progress is reviewed in these areas: nuclear spin-lattice relaxation in ortho-para mixtures of solid deuterium below T/sub lambda/; pulsed NMR experiments of matrix isolated HCl; stimulated Raman scattering in solid hydrogen and nitrogen; and infrared line broadening of matrix isolated molecules

  12. 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...

  13. 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.

  14. Fundamentals of ionic conductivity relaxation gained from study of procaine hydrochloride and procainamide hydrochloride at ambient and elevated pressure.

    Science.gov (United States)

    Wojnarowska, Z; Swiety-Pospiech, A; Grzybowska, K; Hawelek, L; Paluch, M; Ngai, K L

    2012-04-28

    The pharmaceuticals, procaine hydrochloride and procainamide hydrochloride, are glass-forming as well as ionically conducting materials. We have made dielectric measurements at ambient and elevated pressures to characterize the dynamics of the ion conductivity relaxation in these pharmaceuticals, and calorimetric measurements for the structural relaxation. Perhaps due to their special chemical and physical structures, novel features are found in the ionic conductivity relaxation of these pharmaceuticals. Data of conductivity relaxation in most ionic conductors when represented by the electric loss modulus usually show a single resolved peak in the electric modulus loss M(")(f) spectra. However, in procaine hydrochloride and procainamide hydrochloride we find in addition another resolved loss peak at higher frequencies over a temperature range spanning across T(g). The situation is analogous to many non-ionic glass-formers showing the presence of the structural α-relaxation together with the Johari-Goldstein (JG) β-relaxation. Naturally the analogy leads us to name the slower and faster processes resolved in procaine hydrochloride and procainamide hydrochloride as the primary α-conductivity relaxation and the secondary β-conductivity relaxation, respectively. The analogy of the β-conductivity relaxation in procaine HCl and procainamide HCl with JG β-relaxation in non-ionic glass-formers goes further by the finding that the β-conductivity is strongly related to the α-conductivity relaxation at temperatures above and below T(g). At elevated pressure but compensated by raising temperature to maintain α-conductivity relaxation time constant, the data show invariance of the ratio between the β- and the α-conductivity relaxation times to changes of thermodynamic condition. This property indicates that the β-conductivity relaxation has fundamental importance and is indispensable as the precursor of the α-conductivity relaxation, analogous to the relation found

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

    DEFF Research Database (Denmark)

    Jensen, Anders A.; Hansen, Jakob L; Sheikh, Søren P

    2002-01-01

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

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. Kramers degeneracy and relaxation in vanadium, niobium and tantalum clusters

    Science.gov (United States)

    Diaz-Bachs, A.; Katsnelson, M. I.; Kirilyuk, A.

    2018-04-01

    In this work we use magnetic deflection of V, Nb, and Ta atomic clusters to measure their magnetic moments. While only a few of the clusters show weak magnetism, all odd-numbered clusters deflect due to the presence of a single unpaired electron. Surprisingly, for the majority of V and Nb clusters an atomic-like behavior is found, which is a direct indication of the absence of spin–lattice interaction. This is in agreement with Kramers degeneracy theorem for systems with a half-integer spin. This purely quantum phenomenon is surprisingly observed for large systems of more than 20 atoms, and also indicates various quantum relaxation processes, via Raman two-phonon and Orbach high-spin mechanisms. In heavier, Ta clusters, the relaxation is always present, probably due to larger masses and thus lower phonon energies, as well as increased spin–orbit coupling.

  2. Dynamic relaxation method in analysis of reinforced concrete bent elements

    Directory of Open Access Journals (Sweden)

    Anna Szcześniak

    2015-12-01

    Full Text Available The paper presents a method for the analysis of nonlinear behaviour of reinforced concrete bent elements subjected to short-term static load. The considerations in the range of modelling of deformation processes of reinforced concrete element were carried out. The method of structure effort analysis was developed using the finite difference method. The Dynamic Relaxation Method, which — after introduction of critical damping — allows for description of the static behaviour of a structural element, was used to solve the system of nonlinear equilibrium equations. In order to increase the method effectiveness in the range of the post-critical analysis, the Arc Length Parameter on the equilibrium path was introduced into the computational procedure.[b]Keywords[/b]: reinforced concrete elements, physical nonlinearity, geometrical nonlinearity, dynamic relaxation method, arc-length method

  3. Suppressing relaxation in superconducting qubits by quasiparticle pumping.

    Science.gov (United States)

    Gustavsson, Simon; Yan, Fei; Catelani, Gianluigi; Bylander, Jonas; Kamal, Archana; Birenbaum, Jeffrey; Hover, David; Rosenberg, Danna; Samach, Gabriel; Sears, Adam P; Weber, Steven J; Yoder, Jonilyn L; Clarke, John; Kerman, Andrew J; Yoshihara, Fumiki; Nakamura, Yasunobu; Orlando, Terry P; Oliver, William D

    2016-12-23

    Dynamical error suppression techniques are commonly used to improve coherence in quantum systems. They reduce dephasing errors by applying control pulses designed to reverse erroneous coherent evolution driven by environmental noise. However, such methods cannot correct for irreversible processes such as energy relaxation. We investigate a complementary, stochastic approach to reducing errors: Instead of deterministically reversing the unwanted qubit evolution, we use control pulses to shape the noise environment dynamically. In the context of superconducting qubits, we implement a pumping sequence to reduce the number of unpaired electrons (quasiparticles) in close proximity to the device. A 70% reduction in the quasiparticle density results in a threefold enhancement in qubit relaxation times and a comparable reduction in coherence variability. Copyright © 2016, American Association for the Advancement of Science.

  4. Donor-driven spin relaxation in multivalley semiconductors.

    Science.gov (United States)

    Song, Yang; Chalaev, Oleg; Dery, Hanan

    2014-10-17

    The observed dependence of spin relaxation on the identity of the donor atom in n-type silicon has remained without explanation for decades and poses a long-standing open question with important consequences for modern spintronics. Taking into account the multivalley nature of the conduction band in silicon and germanium, we show that the spin-flip amplitude is dominated by short-range scattering off the central-cell potential of impurities after which the electron is transferred to a valley on a different axis in k space. Through symmetry arguments, we show that this spin-flip process can strongly affect the spin relaxation in all multivalley materials in which time-reversal cannot connect distinct valleys. From the physical insights gained from the theory, we provide guidelines to significantly enhance the spin lifetime in semiconductor spintronics devices.

  5. Relaxation of stresses during reduction of anode supported SOFCs

    DEFF Research Database (Denmark)

    Frandsen, Henrik Lund; Chatzichristodoulou, Christodoulos; Jørgensen, Peter Stanley

    2016-01-01

    To assess the reliability of solid oxide fuel cell (SOFC) stacks during operation, the stress field in the stack must be known. During operation the stress field will depend on time as creep processes relax stresses. This work reports further details on a newly discovered creep phenomenon......, accelerated creep, taking place during the reduction of a Ni-YSZ anode. This relaxes stresses at a much higher rate (~×104) than creep during operation. Thus, the phenomenon of accelerated creep during reduction has to be considered both in the production of stacks and in the analysis of the stress field...... of reduction should decrease significantly over minutes. In this work these internal stresses are measured in-situ before and after the reduction by use of X-ray diffraction. This is done by determining the elastic micro-strains (correlating to the stresses), which are assessed from the widening of the Bragg...

  6. Relaxational dissipation of magnetic field energy in a rarefied plasma

    International Nuclear Information System (INIS)

    Vekshtejn, G.E.

    1987-01-01

    A mechanism of solar corona plasma heating connected with relaxation of a magnetic configuration in the corona to the state of the magnetic energy minimum at restrictions imposed by high conductivity of a medium is considered. Photospheric plasma pulsations leading to generation of longitudinal currents in the corona are in this case energy sources. The excess magnetic energy of these currents is dissipated as a result of reclosing of force lines of the magnetic field in narrow current layers. Plasmaturbulence related to the process of magnetic reclosing is phenomenologically described in this case by introducing certain characteristic time of relaxation. Such an approach permits to relate the plasma heating energy with parameters of photospheric motions in the framework of a simple model of the magnetic field

  7. Coaxial helicity injection and n=1 relaxation activity in the HIST spherical torus

    International Nuclear Information System (INIS)

    Nagata, M.; Oguro, T.; Kagei, Y.

    2003-01-01

    In order to understand comprehensively the role of the n=1 instability and relaxation on current generation processes in helicity-driven spherical systems, we have investigated dynamics of ST plasmas produced in the HIST device by decreasing the external toroidal field (TF) and reversing its sign in time. In result, we have discovered that the ST relaxes towards flipped ST configurations through formation of reversed-field pinches (RFPs)-like magnetic field profiles. Surprisingly, it has been observed that not only toroidal flux but also poloidal flux reverses sign spontaneously during the relaxation process. The dynamics associated to self-reversal of the magnetic fields is presently investigated by using three-dimensional magnetohydrodynamic (MHD) numerical simulations. Furthermore, we have first demonstrated that a flipped ST plasma can be successfully sustained by CHI. The n=1 relaxation activity is found to be essential in the current sustainment of the flipped ST as well as the spheromak and the unflipped ST. (author)

  8. 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.

  9. Mechanisms of relaxation and spin decoherence in nanomagnets

    Science.gov (United States)

    van Tol, Johan

    Relaxation in spin systems is of great interest with respect to various possible applications like quantum information processing and storage, spintronics, and dynamic nuclear polarization (DNP). The implementation of high frequencies and fields is crucial in the study of systems with large zero-field splitting or large interactions, as for example molecular magnets and low dimensional magnetic materials. Here we will focus on the implementation of pulsed Electron Paramagnetic Resonance (ERP) at multiple frequencies of 10, 95, 120, 240, and 336 GHz, and the relaxation and decoherence processes as a function of magnetic field and temperature. Firstly, at higher frequencies the direct single-phonon spin-lattice relaxation (SLR) is considerably enhanced, and will more often than not be the dominant relaxation mechanism at low temperatures, and can be much faster than at lower fields and frequencies. In principle the measurement of the SLR rates as a function of the frequency provides a means to map the phonon density of states. Secondly, the high electron spin polarization at high fields has a strong influence on the spin fluctuations in relatively concentrated spin systems, and the contribution of the electron-electron dipolar interactions to the coherence rate can be partially quenched at low temperatures. This not only allows the study of relatively concentrated spin systems by pulsed EPR (as for example magnetic nanoparticles and molecular magnets), it enables the separation of the contribution of the fluctuations of the electron spin system from other decoherence mechanisms. Besides choice of temperature and field, several strategies in sample design, pulse sequences, or clock transitions can be employed to extend the coherence time in nanomagnets. A review will be given of the decoherence mechanisms with an attempt at a quantitative comparison of experimental rates with theory.

  10. Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

    International Nuclear Information System (INIS)

    Minelli, Matteo; Doghieri, Ferruccio

    2014-01-01

    Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps

  11. Autogenic Training Relaxation Helping Postpartum Mothers to Achieve Successful Breastfeeding on Early Lactation Period

    OpenAIRE

    Juanita, Farida

    2013-01-01

    Introduction: The numbers of breastfeeding failures are mostly caused by mothers` disbelief to themselves. One method that can be done to overcome these problems in accordance with the self-care nursing theory is the autogenic training relaxation. This method teaches mothers to be self-sufficient in building a positive intention and motivation to help the process of breastfeeding. This study aimed to examine the influence of autogenic training relaxation to the effectiveness of breastfeeding ...

  12. Vibrational relaxation in liquids: Comparisons between gas phase and liquid phase theories

    International Nuclear Information System (INIS)

    Russell, D.J.

    1990-12-01

    The vibrational relaxation of iodine in liquid xenon was studied to understand what processes are important in determining the density dependence of the vibrational relaxation. This examination will be accomplished by taking simple models and comparing the results to both experimental outcomes and the predictions of molecular dynamics simulations. The vibration relaxation of iodine is extremely sensitive to the iodine potential. The anharmonicity of iodine causes vibrational relaxation to be much faster at the top of the iodine well compared to the vibrational relaxation at the bottom. A number of models are used in order to test the ability of the Isolated Binary Collision theory's ability to predict the density dependence of the vibrational relaxation of iodine in liquid xenon. The models tested vary from the simplest incorporating only the fact that the solvent occupies volume to models that incorporate the short range structure of the liquid in the radial distribution function. None of the models tested do a good job of predicting the actual relaxation rate for a given density. This may be due to a possible error in the choice of potentials to model the system

  13. Influence of the storage conditions on prestressing steel relaxation losses

    Directory of Open Access Journals (Sweden)

    Suárez, F.

    2012-12-01

    Full Text Available Stress relaxation losses on active reinforcement have significant impact on prestressed concrete structures. This is why relaxation tests are carried out on prestressing steel wires and strands after being manufactured. Then, these materials are coiled and stored for a long-term period, sometimes in excess of one year. The influence of these operations, carried out after manufacturing, is usually neglected. Nevertheless, some manufacturers and contractors have noticed that, sometimes, when relaxation tests are carried out after a long-term storage, the relaxation losses found are higher than those measured immediately after manufacturing. In this work, lab tests are performed to check the influence of the coiling radius and the period of storage on the relaxation test. In addition to this, an analytical model is presented to predict the results of a relaxation test carried out on a wire coiled and stored for a long-term period. This model explains the evolution on the cross-sectional stress profile along the coiling-storing-uncoiling process, as well as the influence of the residual stresses on it.

    La pérdida de tensión por relajación en las armaduras activas afecta de forma importante a las estructuras de hormigón pretensado. Por ello se realizan ensayos de relajación de los alambres y cordones de pretensado tras su fabricación. Después, el material es enrollado y almacenado durante periodos que en ocasiones pueden superar el año de duración. Generalmente se desprecia la influencia que estas operaciones posteriores a la fabricación pueden tener sobre el material. Sin embargo, diversos fabricantes y suministradores han constatado experimentalmente que, en ocasiones, el material almacenado durante un periodo prolongado presenta pérdidas de relajación mayores que inmediatamente tras su fabricación. En este trabajo se realizan ensayos de laboratorio para comprobar la influencia que el radio de enrollamiento y el periodo de

  14. Use of relaxation skills in differentially skilled athletes.

    OpenAIRE

    Kudlackova, K.; Eccles, D. W.; Dieffenbach, K.

    2013-01-01

    Objectives: To examine the use of relaxation skills by differentially skilled athletes in relation to the deliberate practice framework. Design: Differentially skilled athletes completed a survey about their use of relaxation skills. Method: 150 athletes representing three skill levels (recreational, college, and professional) completed the deliberate relaxation for sport survey, which assessed relaxation on three deliberate practice dimensions (relevancy, concentration, and ...

  15. The use of (double) relaxation oscillation SQUIDs as a sensor

    NARCIS (Netherlands)

    van Duuren, M.J.; Brons, G.C.S.; Kattouw, H.; Flokstra, Jakob; Rogalla, Horst

    1997-01-01

    Relaxation Oscillation SQUIDs (ROSs) and Double Relaxation Oscillation SQUIDs (DROSs) are based on relaxation oscillations that are induced in hysteretic dc SQUIDs by an external L-R shunt. The relaxation frequency of a ROS varies with the applied flux Φ, whereas the output of a DROS is a dc

  16. Stress relaxation in tempered glass caused by heat soak testing

    DEFF Research Database (Denmark)

    Schneider, Jens; Hilcken, Jonas; Aronen, Antti

    2016-01-01

    Heat soak testing of tempered glass is a thermal process required after the tempering process itself to bring glasses of commercial soda-lime-silica-glass to failure that are contaminated with nickel sulphide inclusions, diameter 50 mm to 500 mm typically. Thus, the tests avoid a so-called "spont...... of commercial soda-lime-silica glass, it causes stress relaxation in tempered glass and the fracture pattern of the glass changes accordingly, especially thin glasses are affected. Based on the Tool-Narayanaswamy-Model, this paper comprises the theoretical background of the stress...

  17. Vibrational relaxation and energy transfer of matrix isolated HCl and DCl

    Energy Technology Data Exchange (ETDEWEB)

    Wiesenfeld, J.M.

    1977-12-01

    Vibrational kinetic and spectroscopic studies have been performed on matrix-isolated HCl and DCl between 9 and 20 K. Vibrational relaxation rates for v = 2 and v = 1 were measured by a tunable infrared laser-induced, time-resolved fluorescence technique. In an Ar matrix, vibrational decay times are faster than radiative and it is found that HCl relaxes about 35 times more rapidly than CCl, in spite of the fact that HCl must transfer more energy to the lattice than DCl. This result is explained by postulating that the rate-determining step for vibrational relaxation produces a highly rotationally excited guest in a V yield R step; rotational relaxation into lattice phonons follows rapidly. HCl v = 1, but not v = 2, excitation rapidly diffuses through the sample by a resonant dipole-dipole vibrational energy transfer process. Molecular complexes, and in particular the HCl dimer, relax too rapidly for direct observation, less than or approximately 1 ..mu..s, and act as energy sinks in the energy diffusion process. The temperature dependence for all these processes is weak--less than a factor of two between 9 and 20 K. Vibrational relaxation of HCl in N/sub 2/ and O/sub 2/ matrices is unobservable, presumably due to rapid V yield V transfer to the host. A V yield R binary collision model for relaxation in solids is successful in explaining the HCl(DCl)/Ar results as well as results of other experimenters. The model considers relaxation to be the result of ''collisions'' due to molecular motion in quantized lattice normal modes--gas phase potential parameters can fit the matrix kinetic data.

  18. Vibrational relaxation and energy transfer of matrix isolated HCl and DCl

    International Nuclear Information System (INIS)

    Wiesenfeld, J.M.

    1977-12-01

    Vibrational kinetic and spectroscopic studies have been performed on matrix-isolated HCl and DCl between 9 and 20 K. Vibrational relaxation rates for v = 2 and v = 1 were measured by a tunable infrared laser-induced, time-resolved fluorescence technique. In an Ar matrix, vibrational decay times are faster than radiative and it is found that HCl relaxes about 35 times more rapidly than CCl, in spite of the fact that HCl must transfer more energy to the lattice than DCl. This result is explained by postulating that the rate-determining step for vibrational relaxation produces a highly rotationally excited guest in a V yield R step; rotational relaxation into lattice phonons follows rapidly. HCl v = 1, but not v = 2, excitation rapidly diffuses through the sample by a resonant dipole-dipole vibrational energy transfer process. Molecular complexes, and in particular the HCl dimer, relax too rapidly for direct observation, less than or approximately 1 μs, and act as energy sinks in the energy diffusion process. The temperature dependence for all these processes is weak--less than a factor of two between 9 and 20 K. Vibrational relaxation of HCl in N 2 and O 2 matrices is unobservable, presumably due to rapid V yield V transfer to the host. A V yield R binary collision model for relaxation in solids is successful in explaining the HCl(DCl)/Ar results as well as results of other experimenters. The model considers relaxation to be the result of ''collisions'' due to molecular motion in quantized lattice normal modes--gas phase potential parameters can fit the matrix kinetic data

  19. Brownian relaxation of an inelastic sphere in air

    Energy Technology Data Exchange (ETDEWEB)

    Bird, G. A., E-mail: gab@gab.com.au [University of Sydney, Sydney, NSW 2006 (Australia)

    2016-06-15

    The procedures that are used to calculate the forces and moments on an aerodynamic body in the rarefied gas of the upper atmosphere are applied to a small sphere of the size of an aerosol particle at sea level. While the gas-surface interaction model that provides accurate results for macroscopic bodies may not be appropriate for bodies that are comprised of only about a thousand atoms, it provides a limiting case that is more realistic than the elastic model. The paper concentrates on the transfer of energy from the air to an initially stationary sphere as it acquires Brownian motion. Individual particle trajectories vary wildly, but a clear relaxation process emerges from an ensemble average over tens of thousands of trajectories. The translational and rotational energies in equilibrium Brownian motion are determined. Empirical relationships are obtained for the mean translational and rotational relaxation times, the mean initial power input to the particle, the mean rates of energy transfer between the particle and air, and the diffusivity. These relationships are functions of the ratio of the particle mass to an average air molecule mass and the Knudsen number, which is the ratio of the mean free path in the air to the particle diameter. The ratio of the molecular radius to the particle radius also enters as a correction factor. The implications of Brownian relaxation for the second law of thermodynamics are discussed.

  20. Relaxation Mechanisms, Structure and Properties of Semi-Coherent Interfaces

    Directory of Open Access Journals (Sweden)

    Shuai Shao

    2015-10-01

    Full Text Available In this work, using the Cu–Ni (111 semi-coherent interface as a model system, we combine atomistic simulations and defect theory to reveal the relaxation mechanisms, structure, and properties of semi-coherent interfaces. By calculating the generalized stacking fault energy (GSFE profile of the interface, two stable structures and a high-energy structure are located. During the relaxation, the regions that possess the stable structures expand and develop into coherent regions; the regions with high-energy structure shrink into the intersection of misfit dislocations (nodes. This process reduces the interface excess potential energy but increases the core energy of the misfit dislocations and nodes. The core width is dependent on the GSFE of the interface. The high-energy structure relaxes by relative rotation and dilatation between the crystals. The relative rotation is responsible for the spiral pattern at nodes. The relative dilatation is responsible for the creation of free volume at nodes, which facilitates the nodes’ structural transformation. Several node structures have been observed and analyzed. The various structures have significant impact on the plastic deformation in terms of lattice dislocation nucleation, as well as the point defect formation energies.