The vibrational excitation of hydrogen fluoride behind incident shock waves

The vibrational excitation of HF occurring behind incident shock waves has been studied in the temperature range of 1400°K to 4100°K. The extent of excitation was determined as a function of time by continuously monitoring the emission intensity from the 1–0 band of HF centered at 2.5 μ. The data were interpreted in terms of the process and gave a value of for M = HF. The corresponding result for (τp)^?1_Ar was found to be insignificant in comparison to this result. Data were also obtained for the effect of F atoms upon the relaxation rate, i.e., it was found that      

Nonbonding pairs in cyclic thioethers: Electrostatic modeling and ab initio calculations for complexes of 2,5-dihydrothiophene,thietane, and thiirane with hydrogen fluoride

Electrostatic potential energies V(ϕ) of a non-perturbing, protonic charge at fixed distances r from the S atom in three cyclic thioethers were examined as functions of the angles ϕ made by the r-vector with the C₂ axis (thiirane and 2,5-dihydrothiophene) or the local C₂ axis (thietane). The electrostatic PE V_HF(ϕ) of HF (HF modelled as an extended electric dipole) was also calculated and the results compared with geometries of the thioether⋯HF complexes calculated at the CCSD(T)-F12c/cc-pVTZ-F12 level. The latter reveal angular deviations θ ∼10-20° of the S⋯H F nuclei from collinearity in directions suggesting secondary interactions of F with H atom(s) of the rings. Angles ϕ made by the S⋯H hydrogen bond with the C₂ (or local C₂) axes in the complexes are systematically larger (∼4-9°) than indicated by the V_HF(ϕ) functions. Minima in the simple V(ϕ) versus ϕ functions occur at values smaller (∼5-10°) than those in the V_HF(ϕ) curves.     

Photon correlation spectroscopy of polystyrene as a function of temperature and pressure

Photon correlation spectroscopy is employed to study the slowly relaxing density and anisotropy fluctuations in bulk atactic polystyrene as a function of temperature from 100 to 160°C and pressure from 1 to 1330 bar. The light-scattering relaxation function is well described by the empirical function ?(t) = exp[?(t/τ)^β], where for polystyrene β = 0.34. The average relaxation time is determined at each temperature and pressure according to 〈τ〉 = (τ/β)Γ(1/β) where Γ(x) is the gamma function. The data can be described by the empirical relation 〈τ〉 = 〈τ〉₀ exp[(A + BP)/R(T ? T₀)] where R is the gas constant and T₀ is the ideal glass transition temperature. The empirical constant A/R is in good agreement with that determined from the viscosity or the dielectric relaxation data (1934 K). The empirical constant B can be interpreted as the activation volume for the fundamental unit involved in the relaxation and is found to be comparable to one styrene subunit (100 mL/mol). The quantity B appears to be a weak function of temperature. The use of pressure as a tool in the study of light scattering near the glass transition now has been established.     

Penning ionization and photoionization electron spectrometry of hydrogen fluoride

An electron spectrometric study has been performed on HF using metastable helium and neon atoms as well as helium and neon resonance photons. High-resolution electron spectra were obtained for a pure He(2³ S) beam, a mixed He(2¹ S, 2³ S) beam, a mixed Ne(3s,³ P ₂,³ P ₀) beam, and for HeI and NeI VUV light. From the comparison of vibrational populations of HF⁺ (X ²£ _i ,v′) and HF⁺ (A ²Σ⁺,v′) produced by He(2³ S) metastables and HeI resonance photons, we conclude that there is only a slight perturbation of the HF (X ¹Σ⁺) potential in He(2³ S) Penning ionization; no perturbation is found for HF⁺ (X ²Π _i ,v′) formation from Ne(³ P _2,0) metastable ionization of HF. For He(2¹ S)+HF theX- andA-ionic state vibrational peak shapes are substantially broader than in the He(2³ S)+HF case pointing to an additional, charge exchanged interaction (He⁺+HF^?) in the entrance channel of the former system. The vibrational population found for NeI _α photoionization of HF for formation of HF⁺ (X ²Π _i ,v′) is found to differ considerably from that for NeI _β photoionization and from the Franck-Condon factors for unperturbed HF(X ¹Σ⁺) and HF⁺ (X ²Π _i ) potentials suggesting the presence of an autoionizing superexcited state of HF in the energy vicinity of the NeI _α resonance photons. The HF⁺ (X)²Π_3/2:²Π_1/2 fine-structure branching ratios vary significantly with the ionizing agent in a similar way as previously found in HCl and HBr.     

Can the Theoretical Fitting of the Proton‐Nuclear‐Magnetic‐Relaxation‐Dispersion (Proton NMRD) Curves of Paramagnetic Complexes Be Improved by Independent Measurement of Their Self‐Diffusion Coefficients?

The self‐diffusion (D_c) coefficients of various lanthanum(III) diamagnetic analogues of open‐chain and macrocyclic complexes of gadolinium used as MRI contrast agents were determined in dilute aqueous solutions (3–31 mM ) by pulsed‐field‐gradient (PFG) high‐resolution ¹H‐NMR spectroscopy. The self‐diffusion coefficient of H₂O (D_w) was obtained for the same samples to derive the relative diffusion constant, a parameter involved in the outersphere paramagnetic‐relaxation mechanism. The results agree with an averaged relative diffusion constant of 2.5 (±0.1)×10^?9 and of 3.3 (±0.1)×10^?9 m² s^?1 at 25 and 37°, respectively, for 'small' contrast agents (M_r 500–750 g/mol), and with the value of bulk H₂O (2.2×10^?9 and 2.9×10^?9 m² s^?1 at 25° and at 37°, respectively) for larger complexes. The use of the measured values of D_c for the theoretical fitting of proton NMRD curves of gadolinium complexes shows that the rotational correlation times (τ_R) are very close to those already reported. However, differences in the electronic relaxation time (τ_SO) at very low field and in the correlation time (τ_V) related to electronic relaxation were found.     

Dielectric relaxation study of N -methyl formamide with glycols using time domain reflectometry technique

The dielectric relaxation study that is static dielectric permittivity (∈₀) and relaxation time (τ) of amide of N-methyl formamide (NMF) with increasing volume percent propylene glycol (PLG) and BLG has been carried out at different temperatures. The time domain reflectometry (TDR) technique has been used to measure reflection coefficient in frequency range of 10 MHz to 20 GHz. The dielectric parameters have been obtained by fitting experimental data with the Havriliak–Negami equation. The experimental observation shows that the static dielectric permittivity and relaxation time decreases with increasing temperature. The experimental observation also shows that the static dielectric permittivity decreases and relaxation time increases with increasing percentage volume of Propylene glycol (PLG) and Butylene glycol (BLG) in NMF. The nature of (?₀) and (τ) is same for the temperature ranges (20, 30, and 40°C). The thermodynamic parameters enthalpy (ΔH) and entropy (ΔS) of the binary mixture are also reported in this work.     

Infrared chemiluminescence in the reactions of atomic fluorine with ethanol,propanol-(2) and some deuterated analogs

In the reactive systems F+C₂H₅OH, F+C₂D₅OD, F+C₂H₅OD, F+(CH₃)₂CHOH, F+(CD₃)₂CHOH, and F+(CD₃)₂CDOH the infrared emission spectra were recorded from HF and/or DF in the fundamental region. Hydrogen abstraction takes place from CH and OH bonds. Vibrational relaxation was suppressed and rotational relaxation took place only to a minor extent. HF(DF) excitation reaches the thermodynamic limit within error limits in all cases. The vibrational distributions of HF for the systems F+(CD₃)₂CHOH, F+(CD₃)₂CDOH show no populati inversion. The vibrational distribution of HF for all other systems and all the DF vibrational distributions obtained show population inversion. Inform theory was used to describe the results of those reaction channels that could be studied separately because of isotopic substitution. The results are c to the systems F + methanol and deuterated analogs investigated before in our laboratory, and to the F+CH₄, F+CD₄, and F+H₂O₂ reactio     

QUANTUM YIELD RATIO OF THE FORWARD and BACK LIGHT REACTIONS OF BACTERIORHODOPSIN T LOW TEMPERATURE and PHOTOSTEADY-STATE CONCENTRATION OF THE BATHOPRODUCT K*

The maximum photosteady state fraction of K, x_K^max, and the ratio of the quantum yields of the forward and back light reactions, trans-bacteriorhodopsin (bR) hArr; K, φ_bR/φ_K, were obtained by measuring the absorption changes produced by illumination of frozen water-glycerol (1:2) suspensions of light-adapted purple membrane at different wavelengths at -165°C. An independent method based on the second derivative of the absorption spectrum in the region of the β-bands was also used. It was found that The quantum yield ratio (0.66 ± 0.06) was found to be independent of excitation wavelength within experimental error in the range510–610 nm. The calculated absorption spectrum of K has its maximum at603–606 nm and an extinction 0.85 ± 0.03 that of bR. At shorter wavelengths there are P-bands at 410, 354 and 336 rim. Using the data of Hurley et al. (Nature 270,540–542, 1977) on relative rates of rhodopsin bleaching and K formation, the quantum yield of K formation was determined to be 0.66 ± 0.04 at low temperature. The quantum efficiency of the back reaction was estimated to be 0.93 ± 0.07. These values of quantum efficiencies of the forward and back light reactions of bR at - 165°C coincide with those recently obtained at room temperature. This indicates that the quantum efficiencies of both forward and back light reactions of bacteriorhodopsin are temperature independent down to -165°C.     

Very short F—H⋯F hydrogen bond in l‐argininium fluoride hydrogen fluoride

There are two symmetry‐independent formula units of the title compound, C₆H₁₅N₄O₂⁺·F^?·HF, per cell. Both cations have a zwitterionic form, protonated at both the guanidyl and amino groups. The two symmetry‐independent cations differ in their conformation. In one of them the C_γ atom is in a gauche position to both the amino and carboxyl groups, while in the other this atom is trans to the amino group. The two anions have very similar geometry. The F^? ions are strongly hydrogen bonded to an HF molecule [F—H?F 2.233 (2) and 2.248 (3) Å], thereby forming an asymmetric non‐linear bifluoride anion. These F?F distances are the shortest reported for an asymmetric HF₂^? anion.     

Relaxation of DF(v = 1) by various polyatomic molecules

By means of the technique of laser-induced fluorescence, the room-temperature vibrational relaxation of DF(v = 1) has been studied in the presence of several polyatomic chaperones. The rate coefficients obtained [in units of (μ;sec·torr)^?1] are CH₄, 0.22; C₂H₆, 0.61; C₄H₁₀, 1.26; C₂H₂, 4.0 × 10^?2; C₂H₂F₂, 1.86 × 10^?2; C₂H₄, 0.175; CH₃F, 0.36; CF₃H, 1.95 × 10^?2; CF₄, 1.0 × 10^?3; CBrF₃, 5.6 × 10^?4; NF₃, 5.1 × 10^?4; SO₂, 1.27 × 10^?2; and BF₃, 7.1 × 10^?3. Results are also reported for vibrational relaxation rate coefficients for HF(v = 1) in the presence of the following chaperones: CH₄, 2.6 × 10^?2; C₂H₆, 5.9 × 10^?2; C₃H₈, 8.4 × 10^?2; and C₄H₁₀, 0.128. A comparison of DF and HF results indicates that for deactivation by C_nH_n+2, rate coefficients for DF are approximately an order of magnitude larger than for HF. The deactivation rate coefficient of DF(v = 1) by CH₄ was found to decrease with increasing temperature between 300 and 740°K.     

Dielectric relaxation study of aniline,N-methylaniline and N,N-dimethylaniline and alcohol in 1, 4-dioxane using picosecond time-domain reflectometry

A time-domain reflectometry technique has been used to measure complex dielectric permittivity ε*(ω) = ε?(ω) ? jε″(ω) of 1-propanol–dioxane, 2-propanol–dioxane, aniline–dioxane, N-methylaniline–dioxane and N,N-dimethylaniline–dioxane mixtures in the frequency range of 10 MHz to 30 GHz. The complex permittivity spectrum has been fitted with a single relaxation time with a small amount of Davidson–Cole behaviour. The least squares fit method has been used to obtain the static dielectric constant (ε₀), relaxation time (τ), Bruggeman factor and Kirkwood correlation factor. The Luzar theoretical model is used to compute the binding energies and average number of hydrogen bond between co-solvent–co-solvent and co-solvent–dioxane molecules.     

Photon correlation spectroscopy of poly(methyl methacrylate) near the glass transition

Poly(methyl methacrylate) (PMMA) has been studied by photon correlation spectroscopy in the temperature range 120–150°C. The relaxation functions for longitudinal density fluctuations were determined and analyzed using the empirical function ?(t) = exp[?(t/τ)^β]. The average relaxation times were calculated for each temperature and compared to mechanical and dielectric relaxation data. The agreement between the various techniques for the primary glass–rubber relaxation was good. The relaxation function observed by light scattering became increasingly broad as the temperature was lowered. This is similar to the results reported previously for poly(ethyl methacrylate) (PEMA). In fact, the light-scattering relaxation function is dominated by the secondary relaxations in these two polymers. Nevertheless, the average relaxation time 〈τ〉 is dominated by the longest relaxation times associated with the primary glass–rubber relaxation.     

Effect of the content of hydrogen fluoride in an etchant on the formation of nanopores in silicon during electrolytic etching

The effect of the HF content on the formation of nanopores in silicon during electrochemical etching was studied. Nanoporous silicon layers were established to be formed only when hydrogen fluoride content in etchants (initial HF content: 49 wt %) was higher than 10–12 vol %. The mass and charge balance of the electrolytic etching of silicon was calculated, and the change in charge number of reaction (effective silicon valence) was determined depending on the HF content. The obtained data were used to propose a silicon etching model with the formation of SiF₄ and nanoporous silicon (where nanopores were formed due to the action of predominantly (HF₂)^? ions).     

Ultrasonic method of determination of stability constants of charge transfer complexes of certain carbonyl compounds and diethylamine in n -hexane

The ultrasonic velocities (U), densities (ρ) and viscosities (η) were measured for solutions containing equimolar concentrations of diethylamine (donor), nine aldehydes and nine ketones (acceptors) in n-hexane at 303 K. Acoustical parameters such as adiabatic compressibility (β), free length (L _f), viscous relaxation time (τ), and molecular interaction parameter (χ_U) have been computed. These values indicate the formation of charge transfer complexes between carbonyl compounds and amine. Formation constant (K) values of the complexes have been evaluated using the equation proposed by Kannappan. The constant values of free energy of activation (ΔG ) and relaxation time indicate the formation of similar charge transfer complexes in these systems. However, the variation in free energy of formation (ΔG°_F) values suggests that their thermodynamic stability depends on the structure of donor and acceptor.     

The density of interface states and their relaxation times in Au/Bi4Ti3O12/SiO2/n‐Si(MFIS) structures

Bismuth titanate (Bi₄Ti₃O₁₂) (BTO) thin films were fabricated on an n‐type Si substrate and annealed by rapid thermal annealing methods. The I‐V measurement shows that the device has properties of Schottky diode with the Φ_B0 of 0.76 eV, n of 2.42, and leakage current of about 10^?7 A at ? 8 V. The experimental C‐V‐f and G/w‐V‐f characteristics of metal‐ferroelectric‐insulator‐semiconductor (MFIS) structures show fairly large frequency dispersion especially at low frequencies due to interface states N_ss. The energy distribution of (N_ss) has been determined by using the high‐low frequency capacitance (C_HF? C_LF) and conductance method. The relaxation time (τ) of interface states was calculated from the conductance method. It has been shown that both the N_ss and relaxation time increase almost exponentially with bias, which activates traps located at deeper gap energies. Copyright © 2011 John Wiley & Sons, Ltd.     

Semiclassical three-dimensional model for vibrational energy transfer in diatomic molecules

A semiclassical model for calculation of rate constants for vibrational excitation in diatomic gases at low temperatures (below 1000 K) is suggested. The model has been tested by its ability to predict the relaxation times of hydrogen (τ_H1 in the temperature region 40–1000 K. The agreement with experimental values is excellent. The isotopic ratio τ_D2/τ_H2 as a function of temperature is predicted.     

Single-Molecule Magnetism in Dy2 Cluster Based on a Schiff Base Ligand

Two dinuclear Ln^III-based clusters, namely [Dy₂L₂(NO₃)₂(DME)₄] ( 1 ) and [Gd₂L₂(NO₃)₂(DME)₄] ( 2 ) [H₂L = (E)-2-((2-hydroxybenzylidene)amino)phenol] were obtained under hydrothermal condition. Two Ln^III ions are bridged by two phenolic hydroxyl oxygen atoms, and the distances of them are 3.829 Å (Dy1–Dy1A) and 3.860 Å (Gd1–Gd1A). Two Dy1–O–Dy1A and Gd1–O–Gd1A angles are 109.4° and 109.8°, respectively. Magnetic studies reveal a weak antiferromagnetic interaction between Gd ions in complex 2 , and single-molecule magnet behavior for 1 with U_eff = 49.9 K and τ₀ = 1.54 × 10^–6 s.     

Crystal Structure and Ferroelectric Evidence of BaZnSi3O8, a Low-Permittivity Microwave Dielectric Ceramic

BaZnSi₃O₈ ceramic was prepared by the conventional solid-state method and sintered at 1100 °C. XRD and synchrotron Rietveld refinement analyses revealed the BaZnSi₃O₈ ceramic presented a monoclinic structure with a space group of P2₁/a (No.14), which is reported for the first time. The BaZnSi₃O₈ ceramic presented a weak ferroelectricity, which was confirmed by the P–E loop and the 90° nanoscale ferroelectric domain. Although ϵ_r–T displayed two ϵ_r abnormal peaks at 400 °C and 460 °C, the Curie temperature (T_c) was located at 460 °C according to the dielectric loss and Curie–Weiss law. Moreover, the BaZnSi₃O₈ ceramic exhibited optimized microwave dielectric properties with ϵ_r=6.55, Q×f=52400 GHz, and τ_f=−24.5 ppm/°C. Hence, the BaZnSi₃O₈ ceramic in the ternary BaO-ZnO-SiO₂ system possessed both weak ferroelectricity and microwave dielectric properties. These results are expected to break the technical barrier of ferroelectric phase shifter applications in microwave and even millimeter-wave frequency bands.     

Échelle d'acidité dans l'hydrogénodifluorure de potassium (KHF2) fondu à 250°C: Détermination électrochimique

In molten potassium hydrogenodifluoride (KHF₂) fully ionized into K⁺ and HF₂^?, at 250°C, the HF₂^? ion is slightly dissociated according to the equilibrium: HF₂^?HF+F^?. This is a solvent acid base equilibrium, HF being the strongest acid and F^? the strongest base in this system. By means of a voltammetric study we showed that the hydrogen electrode may be used as an acidity indicator electrode in the whole acidity range of the melt. By analysis of the equilibrium potential variation in acidic and in basic media, the HF₂^? dissociation constant (melt autoprotolysis constant): K_D = {HF} {F^?} was determined The experimental value: K_D=10^?2.05 mol² kg^?2 is compared with a calculated one, issued from thermodynamic data. Results obtained with other electrodes (LaF₃ monocrystal electrode and copper electrode) were discussed and compared with those obtained with the hydrogen electrode.     

Luminescence and nonradiative relaxation of Pb2+, Sn2+, Sb3+, and Bi3+ in oxide glasses

Absorption and fluorescence spectra of Sn²⁺ and Sb³⁺ in borax, phosphate, and germanate glasses were measured in the temperature range 87–295°K. Fluorescence decay times of these ions in borax glass at 87°K was a single exponent with τ ≈ 6–11 μsec. At 293°K, two decay times were resolved in the range of 50–2000 nsec. The nonexponential behavior is interpreted by the repopulation of the ³P₁ level from the ³P₀ level. The temperature dependence of fluorescence and the low values of quantum efficiencies of fluorescence are explained by means of the configurational coordinate diagram model.