Real time ellipsometry for monitoring plasma-assisted epitaxial growth of GaN

GaN is grown on Si-face 4H-SiC(0 0 0 1) substrates using remote plasma-assisted methods including metalorganic chemical vapour deposition (RP-MOCVD) and molecular beam epitaxy (MBE). Real time spectroscopic ellipsometry is used for monitoring all the steps of substrate pre-treatments and the heteroepitaxial growth of GaN on SiC. Our characterization emphasis is on understanding the nucleation mechanism and the GaN growth mode, which depend on the SiC surface preparation.     

Crystal and molecular structure of thiamine monochloride

The crystal and molecular structure of thiamine monochloride (C₁₂H₁₇N₄OSCl) was determined by X-ray diffraction and refined to a finalR value of 0.042. The compound crystallizes in the monoclinic system, space groupP2₁/a, with cell constantsa=18.929(4),b=11.663(2),c=6.376(2) Å and=96.72(8)°. The thiamine molecule is anhydrous and unprotonated, and the torsion angles at the methylene carbon show that it possesses anF conformation. The dihedral angle value of 84.16(6)° between thiazolium and pyrimidine rings is in the normal range found for the thiamine withF conformation, protonated or not, hydrated or not. Thiamine therefore has the same conformation notwithstanding protonation or hydration, with the rings similarly oriented in all the crystal structures containing thiamine.     

Catalysis in aromatic nucleophilic substitution. Note II. Piperidino substitution reactions of some 2-l-3-nitrothiophenes and 2-l-5-nitrothiophenes in methanol and benzene

The rates of piperidino substitution of some 2-L-3-nitrothiophenes (I) and 2-L-5-nitrothiophenes (II) (L = Cl, Br, I, OC₆H₄NO₂-p, and SO₂Ph) have been measured in methanol and in benzene at various piperidine concentrations. The reactivity of compounds (I) is not affected by the piperidine concentration in both methanol and benzene, except for the case of L = I (Ic). Probably due to association effects, the reactivity of Ic in benzene decreases as the piperidine concentration is increased. The reactions of compounds II follow overall second order kinetics in methanol while in benzene a different behaviour is observed as a function of the nature of the leaving group. In fact, the piperidino substitutions of IIa-c (L = Cl, Br, I) are mildly accelerated at high piperidine concentrations (a moderate solvent effect); on the contrary the reactivity of IId and e shows a strong dependence on the piperidine concentration, pointing out a genuine base catalysis.     

Thermodynamic properties of organic compounds in aqueous solution. II. Apparent molal heat capacities of piperidines,morpholines, and piperazines

Apparent molal heat capacities of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of ΔC _p for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined.     

The inelastic hard dimer gas: a nonspherical model for granular matter

We study a two-dimensional gas of inelastic smooth hard dimers. Since the collisions between dimers are dissipative, being characterized by a coefficient of restitution alpha<1, and no external driving force is present, the energy of the system decreases in time and no stationary state is achieved. However, the resulting nonequilibrium state of the system displays several interesting properties in close analogy with systems of inelastic hard spheres, whose relaxational dynamics has been thoroughly explored. We generalize to inelastic systems a recently method introduced [G. Ciccotti and G. Kalibaeva, J. Stat. Phys. 115, 701 (2004)] to study the dynamics of rigid elastic bodies made up of different spheres held together by rigid bonds. Each dimer consists of two hard disks of diameter d, whose centers are separated by a fixed distance a. By describing the rigid bonds by means of holonomic constraints and deriving the appropriate collision rules between dimers, we reduce the dynamics to a set of equations which can be solved by means of event-driven simulation. After deriving the algorithm we study the decay of the total kinetic energy, and of the ratio between the rotational and the translational kinetic energy of inelastic dimers. We show numerically that the celebrated Haff's homogeneous cooling law t(-2), describing how the kinetic energy of an inelastic hard-sphere system with a constant coefficient of restitution decreases in time, holds even in the case of these nonspherical particles. We fully characterize this homogeneous decay process in terms of appropriate decay constants and confirm numerically the scaling behavior of the velocity distributions.     

Synthesis and stereochemistry of trans- and cis-2,3-difluoro-2,3-dihydrobenzofuran

The geometrical isomers of 2,3-difluoro-2,3-dihydrobenzofuran have been prepared and their structure assigned on the basis of the nmr spectra. Some suggestions on the conformational situation of two adducts are also reported.     

Determination of the substituent effect on the O-H bond dissociation enthalpies of phenolic antioxidants by the EPR radical equilibration technique

The bond dissociation enthalpies (BDE) of several phenols containing electron-withdrawing substituents in the para position have been determined by means of the EPR radical equilibration technique. It has been found that CN, NO(2), CHO, COOR, and COOH induce an increase of the BDE value of the O-H bond, thus producing a worsening of the antioxidant activity of phenols, while Cl, Ph, and CH[double bond]CHPh show an opposite effect. The contributions of these substituents for the calculation of the BDE values in polysubstituted phenols by using the group additivity rule have also been derived. It is shown that this rule provides quite reliable predictions of bond strengths, so that the method can be conveniently used to estimate new data on substituted phenols.     

X-ray structure and circular dichroism of pure rotamers of bis[guanosine-5'-monophosphate(-1)](N,N,N',N'-tetramethylcyclohexyl-1,2-diamine)platinum(II) complexes that have R,R and S,S configurations at the asymmetric diamine

The use of a sterically hindered diamine ligand (Me(4)DACH) has allowed for the first time, the isolation and characterization, both in the solid state (X-ray crystallography) and in solution (circular dichroism), of pure DeltaHT rotamers of [Pt(Me(4)dach)(5'-GMP)(2)] (compounds 1 and 2 for R,R and S,S configurations of the Me(4)DACH ligand, respectively). Comparison of the CD spectra obtained for each rotamer, which differ only in the chirality of the Me(4)DACH ligand (R,R or S,S) or in the chirality of the HT conformation (Delta or Lambda), allowed us to conclude that, in the 200-350 nm range, the contributions to the overall CD spectrum that stem from diamine chirality and diamine-induced chirality of platinum d--d transitions or from sugar chirality are negligible relative to the exciton chiral coupling that occurs for pi-pi* transitions of the cis guanines. Accurate molecular structures of 1.10 D(2)O and 2.14 D(2)O (conventional crystallographic agreement indexes R(1) convergent to 2.07 % and 2.18 %, respectively) revealed that the crystallized rotamers have a DeltaHT conformation that is in agreement with all previously reported X-ray structures of [Pt(diamine)(nucleos(t)ide)(2)] complexes. This conformation allows the 5'-phosphate to be located in proximity to the Me(4)DACH ligand so that (P)O...HC(N) hydrogen-bond interactions exists in both complexes. For both structures, the canting of the guanine planes on the coordination plane is right-handed (R; canting angle (Phi) of 80.9 degrees and 73.2 degrees, respectively); this indicates that the canting direction is driven by the HT conformation chirality (Delta for both compounds) and not by the chirality of the carrier ligand (different for the two compounds). Density functional theory analysis of the conformational space as a function of Phi indicated a good agreement between the computed and experimental structures. The increase in energy for Phi values below 65 degrees and 55 degrees (for 1 and 2, respectively) is mainly due to the short intramolecular contacts between C(8)H and the cis N-Me groups on the same side of the platinum coordination plane.