Theoretical study of the photo-isomerisation reactions of 1,2-dihydro-1,2-phosphaborine and 1,2-dihydro-1,2-alumazaine

The mechanisms of the photochemical isomerisation reactions are investigated theoretically using the model systems, 1,2-dihydro-1,2-phosphaborine (5) and 1,2-dihydro-1,2-alumazaine (6), using the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. For each model reactant, three reaction pathways, which lead to three kinds of photo-isomers, are examined. The structures of the conical intersections, which play a key role in such photo-rearrangements, are determined. The thermal (or dark) reactions of the reactant species are also examined, using the same level of theory, to provide a qualitative explanation of the reaction pathways. These model investigations demonstrate that the preferred reaction route for these two aromatic heterocyclics is as follows: reactant → Franck–Condon region → conical intersection → photoproduct. The theoretical evidences anticipate that after irradiation of 5, the photoproduct yield of the Dewar BP-isomer, 8, should be larger than that of the Dewar BP-isomer, 7, whereas no Dewar BP-isomer 9 can be observed. Moreover, the present theoretical data predict after irradiation of 6, all three Dewar AlN-isomers (10, 11, and 12) and the starting molecule, 6, are produced.     

Amino,ammonio and aminioethenes: a theoretical study of their structure and energetics

We have performed high level ab initio quantum mechanical calculations for aminoethene and the three isomeric 1,1‐ (Z)‐ or (E)‐1,2‐diaminoethenes as well as their singly and doubly charged cations derived by loss of electrons and/or upon protonation. Gas phase molecular structures were computed at the MP2/6‐311 + G(3df,2p) level. Standard molar enthalpies of formation in the gas phase, at T = 298.15 K, were estimated using the G3 composite method and atomization, isodesmic and homodesmotic reactions. Other energetic parameters were also calculated at the G3 level: proton affinities, basicities and adiabatic ionization enthalpies. Theoretical and experimental data are compared. The reported experimental data refer only to aminoethene wherein the standard molar enthalpy of formation has a considerable uncertainty, although the molecular structure is well established. There are no such data, neither structural nor thermochemical, for any of the three isomeric diaminoethenes. Isoelectronic comparisons are made. For example, the diprotonated diaminoethenes are isoelectronic to isobutene and (Z)‐ and (E)‐butene, while the doubly ionized diaminoethenes are likewise related to trimethylenemethane and 1,3‐butadiene. Copyright © 2013 John Wiley & Sons, Ltd.     

Classical Molecular Dynamics Model for Coupled Two‐Component Plasmas – Ionization Balance and Time Considerations

The dynamic properties of ion‐electron two‐component plasmas (TCP) are studied by using classical molecular dynamics (MD) simulations. There is a variety of time dependent and structural results that MD is able to provide in complement to other methods, e.g., useful micro‐field sequences can be generated. The method deals with some specific difficulties: the mass ratio between ions and electrons enforces very small time‐steps appropriate to follow electrons motion while, ions must move significantly in order to build, self consistently, their spatial structure. This results in expensive simulations. Electron trajectories are trapped and de‐trapped with multiple electron collisions around ions resulting in the occurrence of quasi metastable bound electron states. An analysis of micro‐fields at neutral in a hydrogen plasma reveals the need to consider a complete hierarchy of time scales extended typically over 7 order of magnitude, i.e., from a time‐step: ～10^‐19s, to a time required to obtain statistical averages, ～10^‐11s. In order to extend the MD capabilities in representing real coupled plasmas a classical ionization/recombination process has been implemented allowing to follow the evolution of plasmas involving several ion stages and model the ionization balance. Here again TCP simulations deal with extended time‐scale providing information about relaxation of non equilibrium plasma states (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic phase transitions in Nd1 ? xDyxFe3(BO3)4 ferroborates

The magnetic properties of ferroborate single crystals with substituted compositions Nd_{1 − x} Dy _x Fe₃(BO₃)₄ (x = 0.15, 0.25) with competing exchange Nd-Fe and Dy-Fe interactions are investigated. For each composition, we observed a spontaneous spin-reorientation transition from the easy-axis to the easy-plane state and step anomalies on the magnetization curves for the spin-flop transition induced by a magnetic field B | c. The measured parameters and effects are interpreted using a unified theoretical approach based on the molecular field approximation and on calculations performed in the crystal-field model for the rare-earth ion. The experimental temperature dependences of the initial magnetic susceptibility from T = 2 K to T = 300 K, anomalies on the magnetization curves for B | c in fields up to 1.8 T, and their evolution with temperature, as well as temperature and field dependences of magnetization in fields up to 9 T are described. In the interpretation of experimental data, the crystal-field parameters in trigonal symmetry for the rare-earth subsystem are determined, as well as the parameters of Nd-Fe and Dy-Fe exchange interactions.     

Laser-Generated Plasmas as X-Ray Sources in the keV-Range

This report will give an introduction to the X-line emission processes in laser-generated plasmas according to a plasma physical point of view. After a short discussion of the experimental results using laser pulses in the range of ? 10 J and irreadiances of 1 to 100 MW/cm² and of first conclusions about the temperature scaling and the dependence of the emission concerning the atomic number of the target material some models of laser-generated plasmas are analysed. The simple hot-spot model neglects any hydrodynamics and only solves for the rate equations. We discuss the underlying collisional-radiative model and evaluate the numerical results of a more complete model for the spatial and temporal plasma evolution including the hydrodynamics. The applications of such plasmas as small, strong, short sources of X-rays in the keV range is discussed with regard to the lithographic replication of sub-μm structures and to the EXAFS spectroscopy. Laser-generated plasmas are compared with conventional X-ray tubes (with rotating anode) and with synchrotrons. The question of amplified spontaneous emission in the XUV range (superradicant X-ray sources) is only shortly touched upon. In conclusion some comments are given to the recoil momentum effects of the ablating plasma on the target are given (rocket model).     

Quantum dynamics study of isotope effects of the OD/OH + CH3 reactions

ABSTRACT

A six-degrees-of-freedom, time-dependent quantum dynamics calculation is employed to study the integral cross sections, full-dimensional cumulative reaction probabilities and full-dimensional rate constants for the isotopic reactions of the OD and OH with CH₃ reactions. The full-dimensional cumulative reaction probabilities and full-dimensional rate constants are obtained using the energy and J-K shifting approaches based on the six-degrees-of-freedom calculations. The comparison of integral cross sections shows that the OD?+?CH₃ reaction has a larger energy threshold and a smaller tunnelling effect than the OH?+?CH₃ reaction. The corrected rate constants using the experimental zero-point energy have a very good agreement with the experimental results. The comparison of the rate constants shows that the OD?+?CH₃ has smaller rate constants than the OH?+?CH₃ reaction, which indicates a smaller reactivity due to the isotope substitution.     

High pressure catalyzed addition of lactams to siloxydienes

Abstract

Lactams add to Danishefsky's diene 1 yielding N-alkenyl substituted lactams 3-5. The reaction occurs only under pressure (100-300MPa) and, preferentially, in the presence of a mild Lewis acid catalyst such as bismuth chloride or ytterbium triflate. The reactions are fully regioselective and afford linear trans multifunctional 1:1 adducts.     

Energy spectra and angular distribution of projectile-like fragments in 84 MeV <Superscript>12</Superscript>C + <Superscript>169</Superscript>Tm

Kinetic-energy spectra and angular distribution of projectile-like fragments have been measured in the reaction of 84 MeV ¹²C on ¹⁶⁹Tm, using the surface barrier silicon-based ΔE-E telescopes. The fragments close to the projectile show typical spectra of quasi-elastic transfer reactions, which were found to be in agreement with the calculations based on the direct surface transfer reaction model. A significant cross-section of fast alpha-particles was found at forward angles, reminiscent of incomplete fusion reactions, which could be explained in terms of the direct surface transfer reaction model after taking into account the level density of continuum states in the heavy reaction product. The results have been explained in terms of the continuous evolution of the reaction mechanism as a function of the mass transfer. Received: 13 March 2002 / Accepted: 3 May 2002     

An approximate formula for the intermolecular Pauli repulsion between closed shell molecules

The exchange repulsion formula proposed by Murrell and co-workers (Proc. Roy. Soc. (Lond.) 1965, A284, 566; J. chem. Phys., 1967, 47, 4916) is considered in detail. Potentially important terms missing in the formalism of Murrell and co-workers are identified and evaluated for the water dimer using several basis sets. Insights into the contributing terms are obtained by using localized molecular orbitals. The results point towards a relatively simple expression for intermolecular exchange repulsion, based on the isolated wavefunctions of the two overlapping species.     

Rate coefficients and kinetic isotope effects of the abstraction reaction of H atoms from methylsilane

ABSTRACT

Thermal rate constants for chemical reactions using improved canonical variational transition state theory (ICVT) with small-curvature tunnelling (SCT) contributions in a temperature range 180–2000 K are reported. The general procedure is used with high-quality ab initio computations and semi-classical reaction probabilities along the minimum energy path (MEP). The approach is based on a vibrational adiabatic reaction path and is applied to the multiple-channel hydrogen abstraction reaction H + SiH₃CH₃ → products and its isotopically substituted variants. All the degrees of freedom are optimised and harmonic vibrational frequencies and zero-point energies are calculated at the MP2 level with the cc-pVTZ basis set. Single-point energies are calculated at a higher level of theory; CCSD(T)-F12a/VTZ-F12. ICVT/SCT rate constants show that the quantum tunnelling contributions at low temperatures are relatively important and the H-abstraction channel from SiH₃ group of SiH₃CH₃ is the major pathway. The total rate constants are given by the following expression: k_tot(ICVT/SCT) = 2.29 10^?18 T^2.42 exp(?350.9/T) cm³ molec^?1 s^?1. These calculated rates are in agreement with the available experiments. The ICVT/SCT method is further exploited to predict primary and secondary kinetic isotope effects, respectively).     

Density effects of heavy-ion stopping power in high temperature matter

Abstract

The stopping power and range for Xe ions in high temperature matter (partially ionized plasmas) have been calculated using the dielectric response function method. Calculations have been made for a target matter Al (Z = 13) over a wide range of temperatures and densities considering a finite temperature model. The stopping powers obtained have smaller values in comparison with those of a zero temperature model. The stopping power strongly depends on the density and temperature of the target material, and the projectile ion energy.     

The strongest magnetic barrier in the DIII-D tokamak and comparison with the ASDEX UG

Magnetic perturbations in tokamaks lead to the formation of magnetic islands, chaotic field lines, and the destruction of flux surfaces. Controlling or reducing transport along chaotic field lines is a key challenge in magnetically confined fusion plasmas. A local control method was proposed by Chandre et al. [Nucl. Fusion 46, 33–45 (2006)] to build barriers to magnetic field line diffusion by addition of a small second-order control term localized in the phase space to the field line Hamiltonian. Formation and existence of such magnetic barriers in Ohmically heated tokamaks (OHT), ASDEX UG and piecewise analytic DIII-D [Luxon, J.L.; Davis, L.E., Fusion Technol. 8, 441 (1985)] plasma equilibria was predicted by the authors [Ali, H.; Punjabi, A., Plasma Phys. Control. Fusion 49, 1565–1582 (2007)]. Very recently, this prediction for the DIII-D has been corroborated [Volpe, F.A., et al., Nucl. Fusion 52, 054017 (2012)] by field-line tracing calculations, using experimentally constrained Equilibrium Fit (EFIT) [Lao, et al., Nucl. Fusion 25, 1611 (1985)] DIII-D equilibria perturbed to include the vacuum field from the internal coils utilized in the experiments. This second-order approach is applied to the DIII-D tokamak to build noble irrational magnetic barriers inside the chaos created by the locked resonant magnetic perturbations (RMPs) (m, n)=(3, 1)+(4, 1), with m and n the poloidal and toroidal mode numbers of the Fourier expansion of the magnetic perturbation with amplitude δ. A piecewise, analytic, accurate, axisymmetric generating function for the trajectories of magnetic field lines in the DIII-D is constructed in magnetic coordinates from the experimental EFIT Grad-Shafranov solver [Lao, L, et al., Fusion Sci. Technol. 48, 968 (2005)] for the shot 115,467 at 3000 ms in the DIII-D. A symplectic mathematical map is used to integrate field lines in the DIII-D. A numerical algorithm [Ali, H., et al., Radiat. Eff. Def. Solids Inc. Plasma Sc. Plasma Tech. 165, 83 (2010)] based on continued fraction decomposition of the rotational transform labeling the barriers for selecting and identifying the strongest noble irrational barrier is used. The results are compared and contrasted with our previous results on the ASDEX UG. About six times stronger a barrier can be built in the DIII-D than in the ASDEX UG. High magnetic shear near the separatrix in the DIII-D is inferred as the possible cause of this. Implications of this for the DIII-D and the International Thermonuclear Experimental Reactor (ITER) are discussed.     

Synthesis,Physicochemical and Optical Characterization of Novel Fluorescing Complex: <Emphasis Type="Italic">o</Emphasis>-Phenylenediamine—Benzoin

The complex of o-phenylenediamine (o-PDA) and benzoin (BN) was synthesized adopting solid state reaction by mixing of their melt together followed by chilling. The phase diagram study shows the formation of a complex in 1:1 molar ratio with congruent melting point and two eutectics lying on either side of complex. The formation of complex was confirmed using the FTIR, NMR, mass spectroscopy, powder XRD and DSC studies. The optical properties of the parent component, their complex and few other compositions nearby the complex were studied using absorption and laser luminescence techniques. The significantly higher green/yellow emission was noted with newly synthesized complex as compared to that of their parents as well as other compositions of o- PDA and BN.     

Thermal Cross‐Linking of Poly(Vinyl Methyl Ether). III. Rheological Kinetics of Cross‐Linking Reaction

Abstract

The kinetics of the thermally activated cross‐linking reaction of poly(vinyl methyl ether) (PVME) were investigated rheologically by evaluating the viscoelastic material functions such as elastic storage modulus, G′, viscous loss modulus, G″ and complex dynamic viscosity, η*, during the curing process, both isothermally and nonisothermally. The isothermal kinetics reaction was described using a phenomenological equation based on the Malkin and Kulichikhin model, which was predicated originally for the isothermal curing kinetics of thermosetting polymers followed by differential scanning calorimetery (DSC) and was found to be applicable for rheokinetic reactions as well. An excellent representation of the data was obtained using this model; the rate of the reaction was found to be second order regardless of the temperature, which is in good agreement with literature data. The temperature dependence of the cross‐linking rate constant was described by an Arrhenius plot with an apparent activation energy equal to 60–62 kJ mol^?1, in reasonable agreement with the value obtained previously from the temperature dependence of gel time, t _gel. The nonisothermal kinetics reaction rate was described by a model that included the classical rate equation, the Arrhenius equation, and the time–temperature relationships. The apparent activation energy obtained nonisothermally was found to be frequency independent and equal to 72 kJ mol^?1, in very good agreement with the value obtained isothermally from the temperature dependence of t _gel in part II.     

Relativistic corrections for the vibration-rotation levels of the ground electronic state of the hydrogen molecular cation H+ 2

Previous work [Moss, R. E., and Valenzano, L., 2002, Molec. Phys., 100, 649 and 1527] on the non-adiabatic properties of the vibration-rotation levels of the ground electronic state of the hydrogen molecular cation is extended to the calculation of relativistic corrections. Unlike the earlier calculations, in which all matrix elements were evaluated analytically, numerical methods are needed for some of the integrals.     

Parabolic model of the concerted molecular decomposition of chloroalkanes

The intersecting parabolas model (IPM) is used to analyze the measured kinetic parameters for the concerted molecular decomposition of chloroalkanes RCl to olefin and HCl. According to this model, the configuration of the transition state is formed by three atoms: C…H…Cl. The activation energy E and the rate constant k for 12 previously unstudied reactions of concerted molecular decomposition of RCl are calculated based on the enthalpy of reaction by using the IPM algorithms. The factors that influence the activation energy E for RCl decomposition are established: the enthalpy of reaction, energy of stabilization of radical R^?, presence of a π bond adjacent to the reaction center, and dipole–dipole interaction for the decomposition of polychloroalkanes. The values of E and k for reverse reactions of addition of HCl to olefins are evaluated. The energy spectrum of partial activation energies for the concerted molecular decomposition of RCl is constructed.     

Three-body interaction-induced light scattering in krypton gas: a computer simulation of the spectral line shapes

The two-, three- and four-body effective collision induced scattering spectral line shapes are calculated for dense gaseous krypton using the pairwise additivity (PA) approximation and different polarizability models. These spectra and several interaction induced spectra calculated at various densities are compared with the experimental measurements of Barocchi et al. [1988, Europhys. Lett., 5, 607]. The potential effect on the spectrum is found to be weak. The results obtained with the Meinander et al. [1986, J. chem. Phys., 84, 3005] empirical polarizability model and molecular dynamics fit well the experimental two- and three-body spectral shapes. The irreducible contribution to the spectral shape is evaluated using the dipole induced dipole irreducible polarizability [buckingham, A. D., and Hands, I. D., 1991, Chem. Phys. Lett., 185, 544]. This contribution is found to be relatively weak for the anisotropic spectra in the frequency and density range studied, explaining the good agreement between the pairwise approximation calculations and the experimental data. The spectra radiated by the quasi-molecules Kr₂, Kr₃, and Kr₄ (the total spectrum within the PA approximation) are also simulated.     

Equation of state for systems of soft diatomic molecules

A new potential that is a modification of the BBL (Bratko, D.,Blum, L., and Luzar, A.,1985, J. chem. Phys., 83, 6367; Blum, L., Vericat, F., and Bratko, D., 1995, J. chem. Phys., 102, 1461) potential and of the one recently solved analytically by Blum and Vericat (BV) (1995, Molec. Phys., 86, 809; 1996, J. phys. Chem., 100, 1197) is studied by Monte Carlo simulation. The main feature of this potential is that it can be solved using only a small number of parameters (3 in the case treated by BV), and therefore produces a substantial simplification of earlier work. The new potential has an orientational octupole–octupole interaction term which is found necessary to reproduce the broad peak of the oxygen–oxygen structure function due to the tetrahedral position of the second nearest neighbour water molecule. This important feature was absent in the original BBL potential. This model agrees also with the experimental pair correlation functions for oxygen–hydrogen and hydrogen–hydrogen, and yields 42·6 kJ mol^-1 for the internal energy of water, also in agreement with experiment. The hard core central repulsion causes the sharpness of the first peaks in all three correlation functions. This is not necessary but convenient for an analytical solution.     

Assessment of dynamic closure for premixed combustion large eddy simulation

Turbulent piloted Bunsen flames of stoichiometric methane–air mixtures are computed using the large eddy simulation (LES) paradigm involving an algebraic closure for the filtered reaction rate. This closure involves the filtered scalar dissipation rate of a reaction progress variable. The model for this dissipation rate involves a parameter β_c representing the flame front curvature effects induced by turbulence, chemical reactions, molecular dissipation, and their interactions at the sub-grid level, suggesting that this parameter may vary with filter width or be a scale-dependent. Thus, it would be ideal to evaluate this parameter dynamically by LES. A procedure for this evaluation is discussed and assessed using direct numerical simulation (DNS) data and LES calculations. The probability density functions of β_c obtained from the DNS and LES calculations are very similar when the turbulent Reynolds number is sufficiently large and when the filter width normalised by the laminar flame thermal thickness is larger than unity. Results obtained using a constant (static) value for this parameter are also used for comparative evaluation. Detailed discussion presented in this paper suggests that the dynamic procedure works well and physical insights and reasonings are provided to explain the observed behaviour.