Study of surface-bulk mass transport and phase transformation in nano-TiO2 using hyperfine interaction technique

Phase transition from anatase to rutile for the 70 nm TiO₂ crystallite has been investigated by the time differential perturbed angular correlation (TDPAC) technique. The study involved the annealing of the TiO₂ nanocrystals, adsorbed with the nuclear probe (¹⁸¹Hf/¹⁸¹Ta) at trace level, at different temperatures for different durations. The TDPAC measurement was also supported by XRD measurement where the width of the peaks increases with the increase in annealing temperature indicating a crystal growth. The samples annealed up to 823 K for 4 h showed no phase transition, except for the growth of the crystallites. However, it showed phase transition at the same temperature (823 K), when annealed for longer duration, indicating the slower kinetics of the phase transition process. Further the sample, when annealed at 1123 K for 4 h, showed phase transition. It has also been observed that the ¹⁸¹Hf tracer, adsorbed on 70 nm anatase TiO₂, diffuses from surface to bulk during the phase transition process and the extent of diffusion in anatase differs from that in rutile phase. However, surface to bulk mass-transfer is found to play a significant role in the phase transition process.     

J/ψ gluonic dissociation revisited: III. Effects of transverse hydrodynamic flow

In a recent paper [B.K. Patra, V.J. Menon, Eur. Phys. J. C 44, 567 (2005)] we developed a very general formulation to take into account explicitly the effects of the hydrodynamic flow profile on the gluonic breakup of J/ψs produced in an equilibrating quark–gluon plasma. Here we apply that formulation to the case when the medium is undergoing a cylindrically symmetric transverse expansion starting from RHIC or LHC initial conditions. Our algebraic and numerical estimates demonstrate that the transverse expansion causes enhancement of the local gluon number density n_g, affects the p_T-dependence of the average dissociation rate through a partial-wave interference mechanism and makes the survival probability S(p_T) to change with p_T very slowly. Compared to the previous case of a longitudinal expansion the new graph of S(p_T) is pushed up at LHC but develops a rich structure at RHIC, due to a competition between the transverse catch-up time and the plasma lifetime.PACS 12.38.Mh     

Study on the device characteristics of FePc and FePcCl organic thin film Schottky diodes: Influence of oxygen and post deposition annealing

Device characteristics of Al/FePc/Au and Al/FePcCl/Au are performed and found to show rectification properties. The basic diode parameters of the device are determined. The electrical conductivity has been measured both after exposure to oxygen for 20 days and after annealing at temperature up to 473 K. Current density-voltage characteristics under forward bias are found to be due to ohmic conduction at lower voltage regions. At higher voltage regions there is space charge limited conductivity (SCLC) controlled by a discrete trapping level above the valance edge. The electrical parameters of oxygen doped and annealed samples in the ohmic and SCLC region are determined. The reverse bias curves are interpreted in terms of a transition from electrode-limited Schottky emission to the bulk-limited the Poole-Frenkel effect. The Schottky barrier parameters of oxygen doped and annealed structures of FePc and FePcCl are determined from the C²-V characteristics.     

Consequences of spin contamination in unrestricted calculations on open-shell species: effect of Hartree-Fock and Møller-Plesset contributions in hybrid and double-hybrid density functional theory approaches

The extent of spin contamination in unrestricted versions of pure, hybrid and double-hybrid density functional theory (DFT) methods, and its consequences, as manifested in the difference between unrestricted and restricted energies (U - R), has been investigated for 22 homolytic bond dissociation reactions. In accordance with previous studies, increasing the amount of Hartree-Fock (HF) exchange in unrestricted hybrid DFT procedures leads to an increase in the extent of spin contamination. However, in unrestricted double-hybrid DFT procedures, which include both a proportion of HF exchange and a perturbative correlation contribution (MP2), the opposing behavior of UHF and UMP2 with respect to spin contamination leads to smaller differences between the energies predicted by unrestricted and restricted variants. For example, for the most spin-contaminated radicals, a 30-100 kJ mol(-1) |U - R| difference at the HF and MP2 levels is reduced to just 0-5 kJ mol(-1) with the double-hybrid functionals. The double-hybrid UDFT procedures can thus benefit from the inclusion of UHF and UMP2 contributions without incurring to the same extent the problems associated with spin contamination.     

Quantification of Puerarin in Pueraria tuberosa DC. by High-Performance Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC -     

Bond dissociation energies and radical stabilization energies: an assessment of contemporary theoretical procedures

Various contemporary theoretical procedures have been tested for their accuracy in predicting the bond dissociation energies (BDEs) and the radical stabilization energies (RSEs) for a test set of 22 monosubstituted methyl radicals. The procedures considered include the high-level W1, W1', CBS-QB3, ROCBS-QB3, G3(MP2)-RAD, and G3X(MP2)-RAD methods, unrestricted and restricted versions of the double-hybrid density functional theory (DFT) procedures B2-PLYP and MPW2-PLYP, and unrestricted and restricted versions of the hybrid DFT procedures BMK and MPWB1K, as well as the unrestricted DFT procedures UM05 and UM05-2X. The high-level composite procedures show very good agreement with experiment and are used to evaluate the performance of the comparatively less expensive DFT procedures. RMPWB1K and both RBMK and UBMK give very promising results for absolute BDEs, while additionally restricted and unrestricted X2-PLYP methods and UM05-2X give excellent RSE values. UM05, UB2-PLYP, UMPW2-PLYP, UM05-2X, and UMPWB1K are among the less well performing methods for BDEs, while UMPWB1K and UM05 perform less well for RSEs. The high-level theoretical results are used to recommend alternative experimental BDEs for propyne, acetaldehyde, and acetic acid.     

Turbulent Flame Speeds of Premixed Supersonic Flame Kernels

It is unclear whether turbulent flame speed scalings established in low speed regimes are applicable to supersonic flames. To investigate this question, the canonical flame kernel is investigated in a scramjet-like channel having a one degree wall divergence. The growth, shape and internal kernel dynamics are investigated. Results are presented for three Mach numbers, four equivalence ratios, and three turbulence generators. Schlieren photography provides flame images for growth rate statistics and particle image velocimetry (PIV) provides turbulence statistics and investigation of internal kernel dynamics. Supersonic flame kernels are self-propagating and respond to the equivalence ratio in a fashion that is similar to low speed flames. However, supersonic flame kernels have features that are not present in subsonic flame kernels. Baroclinicity, resulting from pressure-density misalignment, creates a reacting vortex ring structure. Further, the mean kernel shape has a Mach number dependence and the vortex ring enhances the turbulent flame speed through entrainment of reactants and augmented flame surface growth. Hence, the previously established (low speed) flame speed scalings are inappropriate for supersonic flame kernels. Drawing motivation from vortex ring literature, the ring propagation velocity is used as the characteristic velocity and a new flame speed scaling is proposed.