Infrared Spectra of Dimethylquinolines in the Gas Phase: Experiment and Theory

Infrared spectra of atmospherically important dimethylquinolines (DMQs), namely 2,4-DMQ, 2,6-DMQ, 2,7-DMQ, and 2,8-DMQ in the gas phase at 80 degrees C were recorded using a long variable path-length cell. DFT calculations were carried out to assign the bands in the experimentally observed spectra at the B3LYP/6-31G* level of theory. The spectral assignments particularly for the C-H stretching modes could not be made unambiguously using calculated anharmonic or scaled harmonic frequencies. To resolve this problem, a scaled force field method of assignment was used. Assignment of fundamental modes was confirmed by potential energy distributions (PEDs) of the normal modes derived by the scaled force fields using a modified version of the UMAT program in the QCPE package. We demonstrate that for large molecules such as the DMQs, the scaling of the force field is more effective in arriving at the correct assignment of the fundamentals for a quantitative vibrational analysis. An error analysis of the mean deviation of the calculated harmonic, anharmonic, and force field fitted frequencies from the observed frequency provides strong evidence for the correctness of the assignment.

A note on the Berry phase for systems having one degree of freedom

A one-dimensional arbitrary system with quantum Hamiltonian H(q, p) is shown to acquire the 'geometric' phase gamma (C)=(1/2) contour integral c(Podqo-qodpo) under adiabatic transport q to q+q+qo(t) and p to p+po(t) along a closed circuit C in the parameter space (qo(t), po(t)). The non-vanishing nature of this phase, despite only one degree of freedom (q), is due ultimately to the underlying non-Abelian Weyl group. A physical realisation in which this Berry phase results in a line spread is briefly discussed.

Unconventional mechanism of stabilization of a tetragonal phase in the perovskite ferroelectric (PbTiO3)(1-x)(BiFeO3)(x)

Temperature-dependent x-ray powder-diffraction study of the tetragonal compositions of PbTiO3-BiFeO3 series has revealed that, unlike for all the known ferroelectric perovskites, the compositions exhibiting giant tetragonality is stabilized from the cubic phase via a complex transition pathway which involve (i) formation of minor monoclinic phase with a large pseudotetragonality along with an intermediate tetragonal phase (major) with a small tetragonality, (ii) gradual vanishing of the intermediate tetragonal phase and concomitant increase in the monoclinic regions, and finally (iii) gradual transformation of the monoclinic phase to the tetragonal phase with giant tetragonality.The system seems to adopt such a complex transition pathway to create amicrostructure with very large number of domains and interfaces for stress relief, which would not have been possible in case of a direct cubic-tetragonal transition.

Electron-Paramagnetic-Res study of LiKSO4 in phase IV below -138 degrees C

A detailed single-crystal EPR study of phase IV of lithium potassium sulphate below -138 degrees C has been carried out using NH3+, which substitutes for K+, as the paramagnetic probe. The spin-Hamiltonian parameters have been evaluated at -140 degrees C and yield an isotropic g=2.0034; (AH)XX=(AH)YY=25.3 G and (AH)ZZ=23.8 G; (AN)XX=8.1 G, (AN)YY=21.2 G and (AN)ZZ=25.9 G. In this phase there are 12 magnetically inequivalent K+ sites and their occurrence is ascribed to the loss of a c glide.

Ferroelastic phase transition in CslO4

An optical investigation of the high-temperature structural phase transition in gel-grown single crystals of CslO4 is reported. This crystal undergoes a phase transition from the room-temperature orthorhombic phase of symmetry Pnma to a tetragonal phase at 150°C. The birefringence Δn = |na-nb| falls abruptly at Tc, indicating the first-order nature of the phase transition. Microscopic examination has revealed the existence of ferroelastic domains in the crystal. The domain structure and its dependence on temperature was studied in detail. The experimental results suggest that this crystal can be assigned to the ferroelastic Aizu species 4/mmmFmmm (p).

Unified large and small signal non-quasi-static model for long channel symmetric DG MOSFET

We propose a unified model for large signal and small signal non-quasi-static analysis of long channel symmetric double gate MOSFET. The model is physics based and relies only on the very basic approximation needed for a charge-based model. It is based on the EKV formalism Enz C, Vittoz EA. Charge based MOS transistor modeling. Wiley; 2006] and is valid in all regions of operation and thus suitable for RF circuit design. Proposed model is verified with professional numerical device simulator and excellent agreement is found. (C) 2010 Elsevier Ltd. All rights reserved.

Thermal expansion and phase transition in NaVO3

The present x-ray study has been undertook in order to correlate the phase transition in sodium metavanadate NaVO3 crystal with its structural aspects. The thermal expansion behaviour of NaVO3 was studied from room temperature up to 500 C, well beyond the transition temperature.

Phase space methods and the Hamilton-Jacobi form of dynamics

A general analysis of the Hamilton-Jacobi form of dynamics motivated by phase space methods and classical transformation theory is presented. The connection between constants of motion, symmetries, and the Hamilton-Jacobi equation is described.

Investigations on Bi2CuO4: a quasi-one-dimensional oxide system

The potential of Bi2CuO4 as the first oxide system to show a linear-chain magnetic behaviour is examined. Electron diffraction studies do not resolve the previously reported ambiguity regarding its space group. The magnetic susceptibility data at high temperatures are best fitted to a uniform antiferromagnetic spin-1/2 Heisenberg chain. At low temperatures, however, neither the uniform nor the alternating Heisenberg antiferromagnetic model fits the data. Magnetic susceptibility data over the entire temperature range can be fitted if one assumes dimeric units with a nearly degenerate second singlet state close to the ground state, these states being separated from an excited triplet state by an energy gap. A simple heuristic model of a dimer that gives such an energy level spectrum is examined.

Computer estimation of the Cd---Hg---Te phase diagram

The compounds CdHgTe and its constituent binaries CdTe, HgTe, and CdHg are semiconductors which are used in thermal, infrared, nuclear, thermoelectric and other photo sensitive devices. The compound CdHgTe has a Sphaleritic structure of possible type A1IIB1IIC6VI. The TERCP program of Kaufman is used to estimate the stable regions of the ternary phase diagram using available thermodynamic data. It was found that there was little variation in stochiometry with temperature. The compositions were calculated for temperatures ranging from 325K to 100K and the compositional limits were Cd13−20Hg12−01Te75−79, Hg varying most. By comparison with a similar compound, Cd In2Te4 of forbidden band width. 88 to .90 e.V., similar properties are postulated for Cd1Hg1Te6 with applications in the infra red region of the spectrum at 300K where this composition is given by TERCP at the limit of stability.

Studies on the phase transitions in thiourea

Thiourea (CS(NH2)2) is one of the few examples of molecular crystals exhibiting ferroelectric properties. The dielectric constant along the ferroelectric axis [100] shows maxima at 169, 177 and 202 K. An inflection point occurs at 170.5 KZ Following Goldsmith and White the phases are named as I (F.E. below 169 K), II (A.F.E. 169 K

Vapor phase oxidation of p-xylene

The kinetics of the vapor phase oxidation of p-xylene over ferric molybdate catalyst were studied in an isothermal, differential, tubular flow reactor in the temperature range of 360 to 420° C. The major product obtained was p-tolualdehyde with small amounts of maleic anhydride and p-toluic acid. No terephthalic acid or CO2 were observed. The reaction rate data collected fit the redox model given by Equation 1. The values of activation energies Ex, Eo and frequency factors Ax, Ao obtained are 72, 63 kJ/mol and 0.64, 2.89 m3/kg catalyst s respectively. The reaction mechanism was established by studying the oxidation of p-tolualdehyde, toluic and terephthalic acids. It is concluded that the reaction follows a parallel-consecutive scheme. On a étudié la cinétique de l'oxydation, en phase gazeuse, du para-xylène sur un catalyseur consistant en molybdate ferrique; cette oxydation s'est faite dans un réacteur à écoulement tubulaire, isothermique et différentiel, dans une échelle de températures comprises entre 360°C et 420°C. Le produit principal obtenu a été le para-tolualdéhyde; on a aussi trouvé de faibles quantités d'anhydride maléique et d'acide para-toluique, mais on n'a pas noté la présence d'acide téréphtalique ni d'anhydride carbonique (CO2). Les résultats obtenus en ce qui a trait à la vitesse de réaction concordent bien avec les données du modèle redox indiquées par l'équation 1. Les valeurs des énergies d'activation Ex et Eo ainsi que des facteurs de fréquence Ax et Ao obtenus sont respectivement 72 et 63 kilojoules/mol. et 0.64 × 103 et 2.89 m3/kg de catalyseur. On a établi le mécanisme de la réaction en étudiant l'oxydation du para-tolualdéhyde et des acides toluique et téréphtalique. On conclut que la réaction se fait d'une manière parallèle et consécutive.

Formant extraction from linear-prediction phase spectra

Extraction of formant information from linear-prediction phase spectra is proposed. It is shown that the derivative of phase spectrum gives reliable formant information. Since the phase spectra for several resonators in cascade are additive, the resonance peaks are additive in the derivative of the phase spectrum unlike in the magnitude spectrum and hence the problem of identifying merged peaks is very easily solved by this method. Application of the method is illustrated through examples of linear-prediction spectra obtained for simulated models and for actural speech segments.