Intrinsic gas-phase electrophilic reactivity of Ccclic N-alkyl- and N-acyliminium ions

he intrinsic gas-phase reactivity of cyclic N-alkyl- and N-acyliminium ions toward addition of allyltrimethylsilane (ATMS) has been compared using MS2 and MS3 pentaquadrupole mass spectrometric experiments. An order of electrophilic reactivity has been derived and found to agree with orders of overall reactivity in solution. The prototype five-membered ring N-alkyliminium ion 1a and its N-CH3 analogue 1b, as well as their six-membered ring analogues 1c and 1d, lack N-acyl activation and they are, accordingly, inert toward ATMS addition. The five- and six-membered ring N-acyliminium ions with N-COCH3 exocycclic groups, 3a and 3b, respectively, are also not very reactive. The N-acyliminium ions 2a and 2c, with s-trans locked endocyclic N-carbonyl groups, are the most reactive followed closely by 3c and 3d with exocyclic (and unlocked) N-CO2CH3 groups. The five-membered ring N-acyliminium ions are more reactive than their six-membered ring analogues, that is:  2a > 2c and 3c > 3d. In contrast with the high reactivity of 2a, its N-CH3 analogue 2b is inert toward ATMS addition. For the first time, the transient intermediates of a Mannich-type condensation reaction were isolatedthe β-silyl cations formed by ATMS addition to N-acyliminium ionsand their intrinsic gas-phase behavior toward dissociation and reaction with a nucleophile investigated. When collisionally activated, the β-silyl cations dissociate preferentially by Grob fragmentation, that is, by retro-addition. With pyridine, they react competitively and to variable extents by proton transfer and by trimethylsilylium ion abstractionthe final and key step postulated for α-amidoalkylation. Becke3LYP/6-311G(d,p) reaction energetics, charge densities on the electrophilic C-2 site, and AM1 LUMO energies have been used to rationalize the order of intrinsic gas-phase electrophilic reactivity of cyclic iminium and N-acyliminium ions.

Anomalous resistivity at the structural phase transition of polycrystalline SnTe

An excess resistivity has been observed in thin film polycrystalline samples of SnTe with low carrier concentration and is attributed to the additional scattering due to the phonon softening associated with the structural phase transition.

Upgrading Bio-Platform Molecules in the Gas-Phase: From Levulinic Acid to Bio-Chemicals

Levulinic acid (LA) is a polyfunctional molecule obtained from biomass. Because of its structure, the United States Department of energy classified LA as one of the top 12 building block chemicals. Typically, it is valorized through chemical reduction to γ-valerolactone (GVL). It is usually done with H2 in batch systems with high H2 pressures and noble metal catalysts, making it expensive and less applicable. Therefore, alternative approaches such as catalytic transfer hydrogenation (CTH) through the Meerwein–Ponndorf–Verley (MPV) reaction over heterogeneous catalysts have been studied. This uses organic molecules (alcohols) which act as a hydride transfer agent (H-donor), to reduce molecules containing carbonyl groups. Given the stability of the intermediate, reports have shown the batch liquid-phase CTH of levulinate esters with secondary alcohols, and remarkable results (GVL yield) have been obtained over ZrO2, given the need of a Lewis acid (LASites) and base pair for CTH. However, there were no reports of the continuous gas-phase CTH of levulinate esters. Therefore, high surface area ZrO2 was tested for gas-phase CTH of methyl levulinate (ML) using ethanol, methanol and isopropanol as H-donors. Under optimized conditions with ethanol (250 ℃), the reaction is selective towards GVL (yield 70%). However, heavy carbonaceous materials over the catalyst surface progressively blocked LASites changing the chemoselectivity. The in situ regeneration of the catalyst permitted a partial recovery of the LASites and an almost total recovery of the initial catalytic behavior, proving the deactivation reversible. Tests with methanol were not promising (ML conversion 35%, GVL yield 4%). As expected, using isopropanol provided complete conversion and a GVL yield of 80%. The reaction was also tested using bioethanol derived from agricultural waste. In addition, a preliminary study was performed for the hydrogenolysis of polyols to produce bioethanol, were Pd-Fe catalyst promoted the ethanol selective (37%) hydrogenolysis of glycerol.

Stability of atomic condensed systems with attractive two-body interactions

In the present report, we review recent investigations that we have conducted on the stability of atomic condensed systems, when the two-body interaction is attractive. In particular, the dynamics that occurs in the condensate due to nonconservative terms is considered in the context of an extension of the mean-field Gross-Pitaevskii approximation. Considering the relative intensity of the nonconservative parameters, chaotic and solitonic solutions are verified. Also discussed is the possibility of a liquid-gas phase transition in the presence of positive three-body elastic collisions.

Atomic Bose-Einstein condensation with three-body interactions and collective excitations

The stability of a Bose-Einstein condensed state of trapped ultra-cold atoms is investigated under the assumption of an attractive two-body and a repulsive three-body interaction. The Ginzburg-Pitaevskii-Gross (GPG) nonlinear Schrodinger equation is extended to include an effective potential dependent on the square of the density and solved numerically for the s-wave. The lowest collective mode excitations are determined and their dependences on the number of atoms and on the strength of the three-body force are studied. The addition of three-body dynamics can allow the number of condensed atoms to increase considerably, even when the strength of the three-body force is very small compared with the strength of the two-body force. We study in detail the first-order liquid-gas phase transition for the condensed state, which can happen in a critical range of the effective three-body force parameter.

Droplet formation in cold asymmetric nuclear matter in the quark-meson-coupling model

The quark-meson-coupling model is used to study droplet formation from the liquid-gas phase transition in cold asymmetric nuclear matter. The critical density and proton fraction for the phase transition are determined in the mean field approximation. Droplet properties are calculated in the Thomas-Fermi approximation. The electromagnetic field is explicitly included and its effects on droplet properties are studied. The results are compared with the ones obtained with the NL1 parametrization of the non-linear Walecka model. © 2000 Elsevier Science B.V.

Quantum vacuum in hot nuclear matter: A non-perturbative treatment

We derive the equation of state for hot nuclear matter using the Walecka model in a non-perturbative formalism. We include here the vacuum polarization effects arising from the nucleon and scalar mesons through a realignment of the vacuum. A ground state structure with baryon-antibaryon condensates yields the results obtained through the relativistic Hartree approximation of summing baryonic tadpole diagrams. Generalization of such a state to include the quantum effects for the scalar meson fields through the σ -meson condensates amounts to summing over a class of multiloop diagrams. The techniques of the thermofield dynamics method are used for the finite-temperature and finite-density calculations. The in-medium nucleon and sigma meson masses are also calculated in a self-consistent manner. We examine the liquid-gas phase transition at low temperatures (≈ 20 MeV), as well as apply the formalism to high temperatures to examine a possible chiral symmetry restoration phase transition.

Warm asymmetric matter in the quark-meson coupling model

In this work we study the warm equation of state of asymmetric nuclear matter in the quark-meson coupling model which incorporates explicitly quark degrees of freedom, with quarks coupled to scalar, vector, and isovector mesons. Mechanical and chemical instabilities are discussed as a function of density and isospin asymmetry. The binodal section, essential in the study of the liquid-gas phase transition is also constructed and discussed. The main results for the equation of state are compared with two common parametrizations used in the nonlinear Walecka model and the differences are outlined.

Quantum oscillations of spin polarization in a GaAs/AlGaAs double quantum well

5 We employ the circular-polarization-resolved magnetophotoluminescence technique to probe the spin character of electron and hole states in a GaAs/AlGaAs strongly coupled double-quantum-well system. The photoluminescence (PL) intensities of the lines associated with symmetric and antisymmetric electron states present clear out-of-phase oscillations between integer values of the filling factor. and are caused by magnetic-field-induced changes in the population of occupied Landau levels near to the Fermi level of the system. Moreover, the degree of circular polarization of these emissions also exhibits the oscillatory behavior with increasing magnetic field. Both quantum oscillations observed in the PL intensities and in the degree of polarizations may be understood in terms of a simple single-particle approach model. The k . p method was used to calculate the photoluminescence peak energies and the degree of circular polarizations in the double-quantum-well structure as a function of the magnetic field. These calculations prove that the character of valence band states plays an important role in the determination of the degree of circular polarization and, thus, resulting in a magnetic-field-induced change of the polarization sign.

Polaron liquid-gas crossover at the orthorhombic-rhombohedral transition of manganites

High-resolution synchrotron x-ray powder diffraction in La(0.7)Ca(0.3)MnO(3) shows in detail a first-order structural phase transition from orthorhombic (space-group Pnma) to rhombohedral (space-group R (3) over barc) crystal structures near T(S)=710 K. Magnetic susceptibility measurements show that the rhombohedral phase strictly obeys the Curie-Weiss law as opposed to the orthorhombic phase. A concomitant change in the electrical resistivity behavior, consistent with an alteration from nonadiabatic to adiabatic small polaron hopping regimes, was also observed at T(S). The simultaneous change in transport and magnetic properties are identified as a transition from a correlated polaron liquid for Tgas for T>T(S), driven by the change in the crystal symmetry.

Dynamic transitions in a three dimensional associating lattice gas model

The aggregation of interacting Brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the concentration range considered. By generalizing Kramers' rate theory to the presence of shear and collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.

Dynamic transitions in a two dimensional associating lattice gas model

Using Monte Carlo simulations we investigate some new aspects of the phase diagram and the behavior of the diffusion coefficient in an associating lattice gas (ALG) model on different regions of the phase diagram. The ALG model combines a two dimensional lattice gas where particles interact through a soft core potential and orientational degrees of freedom. The competition between soft core potential and directional attractive forces results in a high density liquid phase, a low density liquid phase, and a gas phase. Besides anomalies in the behavior of the density with the temperature at constant pressure and of the diffusion coefficient with density at constant temperature are also found. The two liquid phases are separated by a coexistence line that ends in a bicritical point. The low density liquid phase is separated from the gas phase by a coexistence line that ends in tricritical point. The bicritical and tricritical points are linked by a critical lambda-line. The high density liquid phase and the fluid phases are separated by a second critical tau-line. We then investigate how the diffusion coefficient behaves on different regions of the chemical potential-temperature phase diagram. We find that diffusivity undergoes two types of dynamic transitions: a fragile-to-strong transition when the critical lambda-line is crossed by decreasing the temperature at a constant chemical potential; and a strong-to-strong transition when the critical tau-line is crossed by decreasing the temperature at a constant chemical potential.

Combined Monte Carlo and quantum mechanics study of the solvatochromism of phenol in water. The origin of the blue shift of the lowest pi-pi* transition

A combined and sequential use of Monte Carlo simulations and quantum mechanical calculations is made to analyze the spectral shift of the lowest pi-pi* transition of phenol in water. The solute polarization is included using electrostatic embedded calculations at the MP2/aug-cc-pVDZ level giving a dipole moment of 2.25 D, corresponding to an increase of 76% compared to the calculated gas-phase value. Using statistically uncorrelated configurations sampled from the MC simulation,first-principle size-extensive calculations are performed to obtain the solvatochromic shift. Analysis is then made of the origin of the blue shift. Results both at the optimized geometry and in room-temperature liquid water show that hydrogen bonds of water with phenol promote a red shift when phenol is the proton-donor and a blue shift when phenol is the proton-acceptor. In the case of the optimized clusters the calculated shifts are in very good agreement with results obtained from mass-selected free jet expansion experiments. In the liquid case the contribution of the solute-solvent hydrogen bonds partially cancels and the total shift obtained is dominated by the contribution of the outer solvent water molecules. Our best result, including both inner and outer water molecules, is 570 +/- 35 cm(-1), in very good agreement with the small experimental shift of 460 cm(-1) for the absorption maximum.