Theoretical and experimental analysis of N2–H2 stimulated Raman spectra

The paper reports on a detailed study of the N₂–H₂ collisional line broadening coefficient. High resolution stimulated Raman spectra of nitrogen–hydrogen mixtures have been recorded at liquid nitrogen and room temperatures. Corresponding linewidth calculations have been performed at temperatures between 77 and 500?K using the semiclassical Robert and Bonamy model for J rotational quantum numbers varying between 0 and 11. Comparison between experimental data and calculated results shows good agreement at room temperature using an adjusted value for the kinetic diameter.     

Thermal analysis and infrared study of Nb2O5–TeO2 glasses

Tellurite glasses of the xNb₂O₅–(100–x) TeO₂, (3 ≤ x ≤ 20 mol%) system have been prepared and studied by IR spectroscopy and differential thermal analysis to explore the role of Nb₂O₅ on their structure. IR analysis indicates that NbO₆ transforms TeO₄ units into tellurite structural TeO₃ units, with a shift of lattice vibrations towards higher wavenumbers. The stretching force constant of the tellurite structural units increases with Nb₂O₅ content, a feature that is attributed to the higher bond strength and higher coordination number of Nb₂O₅ relative to TeO₂. The crystallization kinetics has been studied under non-isothermal conditions using the formal theory of transformations for heterogeneous nucleation. The crystallization results are analyzed, and both the activation energy of the crystallization process and the crystallization mechanism are characterized. The thermal stability of these glasses are characterized in terms of characteristic temperatures, such as the glass-transition temperature, T _g, the temperature of onset of crystallization, T _in, the temperature corresponding to the maximum crystallization rate, T _p, and two kinetic parameters, K(T _g) and K(T _p). The results reveal that thermal stability increases with increasing Nb₂O₅ content. XRD diffraction of the studied glasses indicates the presence of microcrystallites of α-tellurite, γ-telluride, Nb₂Te₄O₁₃ and an amorphous matrix.     

In situ evolution of Ni environment in magnesium aluminosilicate glasses and glass–ceramics–Influence of ZrO2 and TiO2 nucleating agents

The evolution of Ni²⁺ environment has been systematically investigated using optical and in situ X-ray absorption spectroscopy (XAS) to determine the influence of nucleating agents (TiO₂ and/or ZrO₂) during the formation of spinel in magnesium aluminosilicate glass–ceramics. The results were complemented by in situ X-ray diffraction data. According to XAS and optical spectroscopy, the nature of nucleating agents does not modify significantly the Ni environment in initial glasses. However, it has a relatively strong influence in the observed crystallization sequence. Ni²⁺ ions do not enter the Zr-containing crystalline phase of ZrO₂ or ZrTiO₄ but a Ni²⁺ coordination change from the fivefold coordinated sites, with a small amount of tetrahedral sites in parent glasses, to ^[6]Ni²⁺ and ^[4]Ni²⁺ sites in spinel (in glasses nucleated by ZrO₂ and/or TiO₂) or in β-quartz solid solutions (in glasses nucleated by ZrO₂) has been found.     

Direct Detection of Al–O–Al Structure in Aluminosilicate Specimens: A Use of Homo-Nuclear DQMAS NMR

A general strategy of Al–O–Al structure in various aluminosilicate was evaluated by combining triple-quantum magic angle spinning (3QMAS) and double-quantum homo-nuclear correlation under magic angle spinning (DQMAS) solid-state nuclear magnetic resonance (NMR) measurements with the aid of high magnetic field NMR (800 MHz for ¹H Larmor frequency). The results show that in many cases the direct detection of Al–O–Al sites in aluminosilicate crystals and glasses is possible; hence the extent of aluminum avoidance can be directly elucidated. Specifically, experimental evidence of Al–O–Al linkages in several aluminosilicate materials with Si/Al >1 was straightforwardly confirmed; and the existence of Al–O–Al is considered to have little correlation with the Si/Al ratio, but it may be strongly related to the cation and local structural arrangement. In addition, the presence of tri-clusters of (Si, Al)O₄-tetrahedra in aluminosilicate framework was proposed, which was thought to act as nuclei for formation and incorporation of cations to achieve charge neutrality.     

In situ 1H NMR Study of Nanoreactor Interaction NH3–H2O in Zeolite Nanopores

The interaction between ammonium NH₃ and H₂O molecules in zeolitic nanopores is studied by in situ ¹H nuclear magnetic resonance (NMR) method. The powder and single crystal samples of natural zeolites, heulandites Ca₄[Al₈Si₂₈O₇₂]·24H₂O and clinoptilolite (Na, K,Ca_1/2)₆[Al₆Si₃₀O₇₂], were used as the model system. It is shown that penetration of NH₃ into the zeolitic nanopores is accompanied by disordering of the hydrogen sublattice of zeolitic water and by the fast proton exchange NH₃ + H₂O ? [NH₄]⁺ + [OH]^? characterized by correlation frequency v _c = ~40 kHz. Another nanoreactor interactions are represented by interaction of [NH₄]⁺ ions with exchangeable Na⁺ and Ca²⁺ ions of the zeolitic structure. The slow ionic exchange [NH₄]⁺ → [Na,Ca_1/2]⁺ and binding of [NH₄]⁺ in cationic sites of the framework were visualized by NMR spectroscopy along with stepwise release of (Na,Ca_1/2)OH from zeolitic pores to the external surface of zeolite grains.     

Activation energy and conductivity of glasses in the P2O5–V2O5–Li2O system

The conductivity of glasses in the 50\textP_\text2 \textO_\text5 - x\textV_\text2 \textO_\text5 - ( 50 - x )\textLi_\text2 \textO50{\text{P}}_{\text{2}} {\text{O}}_{\text{5}} - x{\text{V}}_{\text{2}} {\text{O}}_{\text{5}} - \left( {50 - x} \right){\text{Li}}_{\text{2}} {\text{O}} system was studied as a function of temperature and composition. For all compositions, the conductivity variation as a function of temperature followed an Arrhenius type relationship. Isothermal variation of conductivity as a function of composition showed a minimum for a molar ratio x near 20. Probable mechanisms for decrease of conductivity with decrease of vanadium oxide concentration were explained. The minimum in room temperature was attributed to increase of V⁴⁺/V⁵⁺ with decrease of vanadium oxide in specific concentrations of vanadium oxide. Activation energy increased with decrease of V₂O₅ content. This behavior was attributed to increase of average spacing between vanadium ions.     

Heat Transfer and Hydrodynamic Performance Analysis of a Miniature Tangential Heat Sink Using Al2O3–H2O and TiO2–H2O Nanofluids

In this article, thermal and hydrodynamic performances of a miniature tangential heat sink are investigated experimentally by using Al₂O₃–H₂O and TiO₂–H₂O nanofluids. The effects of flow rate and volume concentration on the thermal performance have been investigated for the Reynolds number range of 210 to 1,100. Experimental results show that the average convective heat transfer coefficient increases 14 and 11% and the bottom temperature of the heat sink decreases 2.2°C and 1.6°C by using Al₂O₃–H₂O and TiO₂–H₂O nanofluid instead of pure distilled water, respectively.     

Effect of TiO2 addition on the crystallization of quenched glasses in the SiO2–Al2O3–ZrO2 system

The glass formation in the SiO₂-rich region of the ternary oxide system Al₂O₃–ZrO₂–SiO₂ with MgO, CaO, and TiO₂ as melting aids was analyzed. The crystallization of glasses with different content of TiO₂ and phase evolution with the temperature was studied by X-ray diffraction, infrared, laser Raman spectroscopy and transmission electron microscopy. The use of TiO₂ favored formation and crystallization of the glasses due to the decrease of the viscosity of melts and acting as a nucleating agent. The crystalline phase of t-ZrO₂ was developed at temperatures as low as 880°C whereas in as prepared specimens without TiO₂ its presence was not detected. For the specimens with TiO₂, t-ZrO₂ and mullite were the principal phases at 1000°C. TiO₂ addition did not change the crystallization sequence but decreased the formation temperature of the crystalline phases. Most of Ti⁴⁺ ions entered into t-ZrO₂ and only a small portion in mullite, but the surplus was detected in ZrTiO₄.     

Infrared spectra of acetylene–water complexes: C2D2–H2O,C2D2–HDO,and C2D2–D2O

Infrared spectra of C₂D₂–water complexes are studied in the 4.1 μm region of the C₂D₂ ν₃ fundamental band using a tunable diode laser source to probe a pulsed supersonic slit jet. Relatively large vibrational red shifts (?27.7 to ?28.0 cm^?1) are observed which are more easily interpretable than for the analogous C₂H₂ vibration thanks to the absence of Fermi resonance effects for C₂D₂. Noticeable homogeneous line broadening leads to estimates of upper state predissociation lifetimes of about 0.5, 0.9 and 1.1 ns for C₂D₂–H₂O, –HDO, and –D₂O, respectively. Transitions involving K_a = 0 and 1 levels are observed for C₂D₂–HDO, but there is a puzzling absence of K_a = 1 for C₂D₂–H₂O and C₂D₂–D₂O.     

The 2CH excitation band in C2H2–N2O and 2CH+torsion combination bands in C2H2–N2O and C2H2–CO2

A preliminary analysis of the 2CH excitation band in C₂H₂–N₂O in the 1.5 µm range (K. Didriche, C. Lauzin, P. Macko, M. Herman and W.J. Lafferty, Chem. Phys. Letters 469, 35 (2009).), only considering 117 low J-, and K_a - vibration-rotation lines, is significantly extended thanks to the analysis of new spectra including very regular series of lines with J/K_a up to 31/15. 1271 b-type lines were assigned. Perturbations are briefly discussed. The rotational temperature in the experiments is estimated to be 20?K and the upper state mean half-time is 1.6?ns for non perturbed levels. The previous analyses of the 2CH + torsion band in C₂H₂–N₂O and in C₂H₂–CO₂ (C. Lauzin, K. Didriche, T. Földes and M. Herman, Mol. Phys. 109, 2105 (2011).), are also extended to include 286 and 234 lines, respectively, also correcting for calibration errors. New rotational constants are obtained using a rigid rotor Hamiltonian by simultaneously fitting the ground, 2CH and 2CH + torsion states in C₂H₂–N₂O, and the latter state, only, in C₂H₂–CO₂.     

Dy3+ doped SiO2–B2O3–Al2O3–NaF–ZnF2 glasses: An exploration of optical and gamma radiation shielding features

A series of Dy³⁺ doped zinc-aluminoborosilicate glasses with chemical composition 30SiO₂-(30-x) B₂O₃–10Al₂O₃–15NaF–15ZnF₂-xDy₂O₃ (x = 0, 0.5, 0.7, 1.0 and 1.5 mol %) were prepared by conventional melt-quenching method. Structural and optical properties of the glasses were analyzed through XRD, FTIR, UV–Visible–NIR and luminescence studies. Gamma radiation shielding parameters were obtained using PSD software. Nephelauxetic ratio (β) and bonding parameters (δ) calculated using absorption spectrum shows the decreasing ionic nature of the Dy ions. Judd-Oflet parameters (Ω₂, Ω₄ and Ω₆) obtained shows the covalency and asymmetric nature of dysprosium ions. The luminescence properties shows that Dy³⁺ doped glasses have two strong intense emission at blue (482 nm) and yellow (575 nm) region. Branching ratio and stimulated emission cross section calculated suggests the glasses suitability to act as lasing material. CIE colour coordinates and its colour correlated temperature (CCT) for the glasses were estimated and found that these prepared glasses lie in the warm white light region.     

Stability and stabilization of 2H martensite in Cu–Zn–Al single crystals

The stabilization of the 2H martensitic phase in Cu–Zn–Al single crystals with an electron concentration e/a?=?1.53 was investigated. This orthorhombic 2H martensite was first induced from the cubic β phase by the direct β?→?2H or the indirect β?→?18R?→?2H transformations. On loading the 2H martensite, a transition without hysteresis is observed at a stress which was denoted σ_T1. It was found that this stress is associated with a change in the behaviour of the 2H martensite. A high stabilization of the 2H martensite, around 300?K, is only obtained if an ageing is performed at a stress above σ_T1. Additionally, the stresses of the transformation to another martensitic phase, called 18R₂, were found to be constant when the value of σ_T1 is below the retransformation stress. The 2H martensite and its behaviour on ageing were studied by dilatometry, calorimetry, mechanical testing, optical microscopy and transmission electron microscopy (TEM). Models accounting for the stabilization of the 2H martensite on ageing are proposed.     

Interpretation of 1H and 2H spin–lattice relaxation dispersions: Insights from molecular dynamics simulations of polymer melts

We demonstrate that molecular dynamics simulations are a versatile tool to ascertain the interpretation of spin–lattice relaxation data. For ¹H, our simulation approach allows us to separate and to compare intra- and inter-molecular contributions to spin–lattice relaxation dispersions. Dealing with the important example of polymer melts, we show that the intramolecular parts of ¹H spectral densities and correlation functions are governed by rotational motion, while their inter-molecular counterparts provide access to translational motion, in particular, to mean-squared displacements and self-diffusion coefficients. Exploiting that the full microscopic information is available from molecular dynamics simulations, we determine the range of validity of experimental approaches, which often assume Gaussian dynamics, and we provide guidelines for the determination of free parameters required in experimental analyses. For ²H, we examine the traditional methodology to extract correlation times of complex dynamics from relaxation data. Furthermore, based on knowledge from our computational study, it is shown that measurement of ²H spin–lattice relaxation dispersions allows one to disentangle the intra- and inter-molecular contributions to the corresponding ¹H data in experimental work. Altogether, our simulation results yield a solid basis for future ¹H and ²H spin–lattice relaxation analysis.     

Rovibrational spectra of the Ar–D2O and Kr–D2O van der Waals complexes in the v2 bend region of D2O

Rovibrational spectra of Ar–D₂O and Kr–D₂O complexes are measured in the v₂ bend region of D₂O monomer using a tunable mid-infrared diode laser spectrometer. One para and two ortho bands for both complexes are identified and then analyzed in terms of a nearly free internal rotor model. Molecular constants for the excited vibrational states, including band-origin, rotational and centrifugal distortion constants, and Coriolis coupling constant, are determined accurately. A comparison of the observed band-origins of Ar–D₂O and Kr–D₂O with the previous results of Ne–D₂O shows regular trends of shift from Kr–D₂O to Ne–D₂O.     

The absorption spectrum of H2 18O in the range 13400–14460 cm?1

Using a Fourier-transform spectrometer, we have measured the absorption spectrum of H₂ ¹⁸O vapor in the range 13400?C14460 cm^?1 at room temperature with a resolution of 0.03 cm^?1 and a threshold sensitivity in absorption of 10^?6 cm^?1. With a multipass cell, the volume of which was 3 L and the base of which was 25 cm, a length of the absorbing layer of 10 m has been achieved. A high signal-to-noise ratio, on the order of 1000, has allowed us to detect about 700 lines of the H₂ ¹⁸O molecule, the intensities of which were as low as 10^?25 cm/molecule, at 296 K. The observed lines have been attributed to eleven vibrational-rotational bands of the molecule.     

Prediction of the 1H NMR spectra of epoxy-fused cyclopentane derivatives by calculations of chemical shifts and spin–spin coupling constants

¹H NMR spectra of epoxy-fused cyclopentane derivatives have been computationally investigated with density functional calculations in order to unravel the shielding effect of the epoxy ring on the ¹H NMR chemical shifts of N-substituted epoxy-fused cyclopentane-3, 5-diol derivatives. Both ¹H NMR chemical shifts and spin–spin coupling constants have been calculated with the WP04/cc-pVTZ level of theory in solution. The WP04/cc-pVTZ// B3LYP/6-31+G(d) methodology has been found to reproduce the best experimental results on epoxy-fused cyclopentane derivatives. This study is expected to lead experimentalists in their endeavour to characterize epoxy-fused cyclic systems with ease.     

The low-temperature 13C and 2H spectra and relaxation rates of methyl groups depend on the azimuth of B0 in the molecular frame. Those of 1H do not. Why?

It is shown that the answer to the question asked in the title is: Because the axial symmetry axes of the H-H dipolar coupling tensors in a -CH3 group are perpendicular to the (assumed) threefold axis of the group. By contrast, those of the 13C-H dipolar and 2H quadrupolar coupling tensors are not. The use of "symmetry adapted" spin functions and of a symmetry adapted form of the (dipolar) coupling Hamiltonian greatly simplifies the analysis.     

Luminescence and absorption of Tb3+in mo·Al2O3·B2O3·Tb2O3 glasses

Quantum yields of the green Tb luminescence for 254 nm excitation of glass compositions in the system MO·Al₂O₃· B₂O₃·Tb₂O₃ (M = Mg, Ca, Sr, Ba and Zn) were studied in relation to absorption and excitation spectra. Yields as high as 80% were observed. The Tb 4f-5d absorption maximum ranges from 218 to 232 nm, always at a longer wavelength than the glass matrix absorption. The yield strongly depends on the spectral position of the 4f-5d absorption, due to competing impurity absorption at 254 nm.