H, C NMR and JCH coupling constants investigation of 4-Phenylpyridine: A combined experimental and theoretical study

Proton coupled and uncoupled ¹³C, ¹H, DEPT, COSY and HETCOR NMR spectra of 4-Phenylpyridine (4-Phpy) have been reported for the first time except for its ¹H NMR spectrum. In order to provide a precise structural elucidation for carbon atoms those have very close chemical shifts to each other, the magnitude of ⁿJ_CH (n=1,2,3) coupling constants of 4-Phpy (C₁₁H₉N) have also been investigated. ¹³C, ¹H NMR chemical shifts and ^1-3J_CH coupling constants of 4-Phpy have been calculated by means of B3LYP density functional method with 6-311++G(d,p) basis set. Moreover, the optimized parameters (bond lengths, bond and torsion angles) of 4-Phpy have been calculated with B3LYP at 6-31G(d) level in methanol (ε=32.63). Comparison between the experimental and the theoretical results indicates that density functional B3LYP method is able to provide satisfactory results for predicting NMR properties.     

Structural,electrical and optical properties of Ge implanted GaSe single crystals grown by Bridgman technique

Structural, optical and electrical properties of Ge implanted GaSe single crystal have been studied by means of X‐Ray Diffraction (XRD), temperature dependent conductivity and photoconductivity (PC) measurements for different annealing temperatures. It was observed that upon implanting GaSe with Ge and applying annealing process, the resistivity is reduced from 2.1 × 10⁹ to 6.5 × 10⁵ Ω‐cm. From the temperature dependent conductivities, the activation energies have been found to be 4, 34, and 314 meV for as‐grown, 36 and 472 meV for as‐implanted and 39 and 647 meV for implanted and annealed GaSe single crystals at 500°C. Calculated activation energies from the conductivity measurements indicated that the transport mechanisms are dominated by thermal excitation at different temperature intervals in the implanted and unimplanted samples. By measuring photoconductivity (PC) measurement as a function of temperature and illumination intensity, the relation between photocurrent (I_PC) and illumination intensity (Φ) was studied and it was observed that the relation obeys the power law, I_PC αΦⁿ with n between 1 and 2, which is indication of behaving as a supralinear character and existing continuous distribution of localized states in the band gap. As a result of transmission measurements, it was observed that there is almost no considerable change in optical band gap of samples with increasing annealing temperatures for as‐grown GaSe; however, a slight shift of optical band gap toward higher energies for Ge‐implanted sample was observed with increasing annealing temperatures. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of CdCl2 treatment on properties of CdTe thin films grown by evaporation at low substrate temperatures

The structural, morphological and optical properties of vacuum‐evaporated CdTe thin films were investigated as a function of substrate temperature and post‐deposition annealing without and with CdCl₂/treatment at 400°C for 30 min. Diffraction patterns are almost the same exhibiting higher preferential orientation corresponding to (111) plane of the cubic phase. The intensity of the (111) peak increased with the CdCl₂/annealing treatment. The microstructure observed for all films following the CdCl₂/annealing treatment are granular, regardless of the as‐deposited microstructure. The grain sizes are increased after the CdCl₂/annealing treatment but now contain voids around the grain boundaries. The optical band gaps, E_g, were found to be 1.50, 1.50 and 1.48 eV for films deposited at 200 K and annealed without and with CdCl₂/treatment at 400°C for 30 min respectively. A progressive sharpening of the absorption edge upon heat treatment particularly for the CdCl₂/treated was observed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase equilibrium measurements of acoustically levitated squalane–CO2 mixtures by Raman spectroscopy

This work describes the phase equilibrium measurements of acoustically levitated binary mixtures with concentration measurements using Raman spectroscopy without sample extraction of the autoclave. The levitator design is implemented in a Single‐Droplet Optical Cell for levitation processes under varying atmospheres. The advantages of acoustic levitation of small droplets under increased temperatures and pressure combined with spectroscopic applications like Raman spectroscopy enable novel experiments possibly relevant to the fields of chemical engineering. To the author's knowledge, this is the first use of Raman spectroscopy for phase equilibria investigations on acoustically levitated droplets under high pressure and temperature. The results show very good agreements with literature data. Copyright © 2014 John Wiley & Sons, Ltd.     

Vibrational investigation of 1-cyclopentylpiperazine: A combined experimental and theoretical study

FT-IR and Raman spectra of 1-cyclopentylpiperazine(1cppp)have been experimentally examined in the region of 4000–200cm-1.The optimized geometric parameters,conformational equilibria,normal mode frequencies and corresponding vibrational assignments of 1cppp(C9H18N2)are theoretically examined by means of B3LYP hybrid density functional theory(DFT)method together with 6-31++G(d,p)basis set.On the basis of potential energy distribution(PED)reliable vibrational assignments have been made and the thermodynamics functions,highest occupied and lowest unoccupied molecular orbitals(HOMO and LUMO)of 1cppp have been predicted.Calculations are employed for four different conformations in C1 and Cs point groups of 1cppp in gas phase.Comparison between the experimental and theoretical results indicates that B3LYP method is able to provide satisfactory results for predicting vibrational frequencies and the structural parameters,vibrational frequencies and assignments.Furthermore,C1(equatorial-axial)point group has been found as the most stable conformer of 1cppp.     

Intercalation of graphite and hexagonal boron nitride by lithium

Although graphite and hexagonal form of BN (h-BN) are isoelectronic and have very similar lattice structures, it has been very difficult to intercalate h-BN while there are hundreds of intercalation compounds of graphite. We have done a comparative first principles investigation of lithium intercalation of graphite and hexagonal boron nitride to provide clues for the difficulty of h-BN intercalation. In particular lattice structure, cohesive energy, formation enthalpy, charge transfer and electronic structure of both intercalation compounds are calculated in the density functional theory framework with local density approximation to the exchange-correlation energy. The calculated formation enthalpy of the considered forms of Li intercalated h-BN is found to be positive which rules out h-BN intercalation without externally supplied energy. Also, the Li(BN)₃ form of Li-intercalated h-BN is found to have a large electronic density of states at the Fermi level and an interlayer state that crosses Fermi level at the zone center; these properties make it an interesting material to investigate the role of interlayer states in the superconductivity of alkali intercalated layered structures. The most pronounced change in the charge distribution of the intercalated compounds is found to be charge transfer from the planar σ states to the π states.     

Adsorption Mechanisms of 6-Chloro-3-Hydroxy-2-Pyrazinecarboxamide on Pristine,Si- and Al-Doped C<Subscript>60</Subscript> Fullerenes: A DFT Study

Fullerenes have been of research interest and they have been particularly studied for their possible applications as drug delivery vehicles. In the present research, the optimized molecular geometries, electronic properties and the possible interaction mechanisms between C₆₀, Si- or Al-doped C₆₀ and 6-chloro-3-hydroxy-2-pyrazinecarboxamide were investigated using quantum mechanical calculations. The calculated binding energies to the Si- and Al-doped fullerenes suggest that doping of fullerene nanocage enhances the interaction mechanism and alters the chemical and electronic properties. The results and parameters found in this research reveal further insight into drug delivery systems.     

FT-IR and NMR investigation of 2-(1-cyclohexenyl)ethylamine: a combined experimental and theoretical study

FT-IR and (1)H, (13)C, DEPT, HETCOR, COSY, and NOESY NMR spectra of 2-(1-cyclohexenyl)ethylamine (CyHEA) have been reported for the first time. The vibrational frequencies and (1)H, (13)C NMR chemical shifts of CyHEA (C(8)H(15)N) have been calculated by means of the Hartree-Fock (HF), Becke-Lee-Yang-Parr (BLYP) and Becke-3-Lee-Yang-Parr (B3LYP) density functional methods with 6-31 G(d) and 6-31 G(d,p) basis sets, respectively. The comparison between the experimental and the theoretical results indicates that density functional B3LYP method is superior to the scaled HF and BLYP approach for vibrational frequencies and predicting NMR properties.     

Density functional theory study on the identification of 3-[(2-morpholinoethylimino)methyl]benzene-1,2-diol

This study deals with the identification of a title compound, 3-[(2-morpholinoethylimino)methyl]benzene-1,2-diol by means of quantum chemical calculations. The optimized molecular structures, vibrational frequencies and corresponding vibrational assignments, thermodynamic properties, charge analyses, nuclear magnetic resonance (NMR) chemical shifts and ultraviolet-visible (UV-vis) spectra of the title molecule in the ground state were evaluated using density functional theory (DFT) with the standard B3LYP/6-311++G(d,p) method and basis set combination for the first time. Theoretical vibrational spectra of the title compound were interpreted with the aid of normal coordinate analysis based on scaled density functional force field. The results show that the obtained optimized geometric parameters (bond lengths, bond angles and bond dihedrals) and vibrational frequencies were observed to be in good agreement with the available experimental results. Moreover, the calculations of the electronic spectra, (13)C and (1)H chemical shifts were compared with the experimental ones. Furthermore, we not only simulated the frontier molecular orbitals (FMO) and molecular electrostatic potential (MEP) but also determined the transition states and energy band gaps, as well. It was found that charge analyses supported the evidences of MEP. Infrared intensities and Raman activities were also reported.     

Origin of lyotropic liquid crystalline mesophase formation and liquid crystalline to mesostructured solid transformation in the metal nitrate salt-surfactant systems

The zinc nitrate salt acts as a solvent in the ZnX-C(12)EO(10) (ZnX is [Zn(H(2)O)(6)](NO(3))(2) and C(12)EO(10) is C(12)H(25)(OCH(2)CH(2))(10)OH) lyotropic liquid crystalline (LLC) mesophase with a drastic dropping on the melting point of ZnX. The salt-surfactant LLC mesophase is stable down to -52 °C and undergoes a phase change into a solid mesostructured salt upon cooling below -52 °C; no phase separation is observed down to -190 °C. The ZnX-C(12)EO(10) mesophase displays a usual phase behavior with an increasing concentration of the solvent (ZnX) in the media with an order of bicontinuous cubic(V(1))-2D hexagonal(H(1))--a mixture of 2D hexagonal and micelle cubic(H(1) + I)-micelle cubic(I)-micelle(L(1)) phases. The phase behaviors, specifically at low temperatures, and the first phase diagram of the ZnX-C(12)EO(10) system was investigated using polarized optical microscopy (POM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and Raman techniques and conductivity measurements.