CARS studies of vibrationally excited nitrogen at low pressures

Coherent anti-Stokes Raman spectroscopy (CARS) was used to measure the vibrational temperature of microwave-excited nitrogen in a N₂–CO–He mixture. CARS spectra, originating from the N₂-vibrational levelsv=0 up tov=3, have been recorded by both narrowband scanning of the resonance region as well as by broadband OSA detection. For the microwave-excited N₂ molecules a vibrational temperatureT _v (N ₂ = (2130±110K) and a lower limit of detection forN ₂(v = 3) = 1.2 x 10¹⁵ cm^–3 was established. The CARS results were independently confirmed by simultaneously recorded and spectrally resolved CO infrared fluorescence studies.     

Conductance studies of NaCl, KCl, NaBr, NaI, NaBPh4, Bu4NI and NaClO4 in water + 2-methoxyethanol mixtures at 298.15 K

The electrical conductances of the solutions of sodium chloride (NaCl), potassium chloride (KCl), sodium bromide (NaBr), sodium iodide (NaI), sodium tetraphenylborate (NaBPh₄), tetrabutylammonium iodide (Bu₄NI) and sodium perchlorate (NaClO₄) in water (1) + 2-methoxyethanol (2) mixtures containing 0.01, 0.025, 0.05, 0.075, 0.10, 0.15 and 0.20 mol fractions of 2-methoxyethanol have been reported at 298.15 K. The conductance data have been analyzed by the Fuoss–Justice equation. The individual limiting ionic conductivities of Na⁺, K⁺, Bu₄N⁺, BPh₄⁻, I⁻, Cl⁻, and Br⁻ ions have been determined using the Fuoss–Hirsch assumption. The dependencies of the limiting molar conductances, Λ_o, and Walden products, Λ_oη, versus mixed solvent composition have been discussed.     

Infrared absorption of silane,ammonia, acetylene and diborane in the range of the CO2 laser emission lines: Measurements and modelling

Absorption spectra of the gases SiH₄, NH₃, C₂H₂ and of SiH₄/Ar and SiH₄/B₂H₆ mixtures have been measured in the spectral range of the CO₂ laser from 9.2 to 10.8 µm. In agreement with literature, silane shows the highest absorption (absorption coefficient = 3.3 × 10^–2 Pa^–1 m^–1). The deviation of the measured absorption behaviour of silane from literature, as far as the pressure dependence is concerned, can be explained by the enhanced spectral energy density in our experiment. This is confirmed by a rate-equation model involving the basic mechanisms of V-V and V-T energy transfer between vibrationally excited silane molecules. In contrast to silane, the absorption coefficient of NH₃ at the 10P(20) laser line is 4.5 × 10^–4 Pa^–1 m^–1 atp = 20 kPa and has its maximum of 4.5 × 10^–3 Pa^–1 m^–1 at the 10R(6) laser line. For C₂H₂ and B₂H₆, is even less ( 2.1 Ò 10^–5 Pa^–1 m^–1 for C₂H₂).     

CARS methane spectra: Experiments and simulations for temperature diagnostic purposes

CARS laboratory experiments were done in the 2905–2925 cm⁻¹ range, in the vicinity of the ν₁ band of the methane molecule, for pressures ranging from 1 to 50 bar, and temperatures up to 1100 K. These experiments were carried out in order to retrieve the pressure evolution of the CH₄ spectrum, as well as to confirm its temperature dependance. After a brief recall on the theory used to compute pressure broadening coefficients and relaxation rates, we consider the ν₃ and ν₄ infrared bands of methane for benchmark calculations purposes. Next, we present recent experimental CARS spectra and calculated ones. Lastly, we discuss flame experiments as well as comparisons of temperature retrieval using N₂ and CH₄ as probe molecules.     

Coherent Raman and Infrared Studies of Sulfur Trioxide

High-resolution (0.001 cm⁻¹) coherent anti-Stokes Raman scattering (CARS) was used to observe the Q-branch structure of the IR-inactive ν₁ symmetric stretching mode of ³²S¹⁶O₃ and its various ¹⁸O isotopomers. The ν₁ spectrum of ³²S¹⁶O₃ reveals two intense Q-branches in the region 1065–1067 cm⁻¹, with surprisingly complex vibrational–rotational structure not resolved in earlier studies. Efforts to simulate this with a simple Fermi-resonance model involving ν₁ and 2ν₄ states do not reproduce the spectral detail, nor do they yield reasonable spectroscopic parameters. A more subtle combination of Fermi resonance and indirect Coriolis interactions with nearby states, 2ν₄(1=0, ±2), ν₂+ν₄(1=±1), 2ν₂(1=0), is suspected and a determination of the location of these coupled states by high-resolution infrared measurements is under way. At medium resolution (0.125 cm⁻¹), the infrared spectra reveal Q-branch features from which approximate band origins are estimated for the ν₂, ν₃, and ν₄ fundamental modes of ³²S¹⁸O₃, ³²S¹⁸O₂¹⁶O, and ³²S¹⁸O¹⁶O₂. These and literature data for ³²S¹⁶O₃ are used to calculate force constants for SO₃ and a comparison is made with similar values for SO₂ and SO. The frequencies and force constants are in excellent agreement with those obtained by Martin in a recent ab initio calculation.     

Fourier transform emission spectroscopy of the TiF radical in the 407 nm region

Ultraviolet emission spectra of the TiF radical in the 407 nm region have been observed at a resolution of 0.04 cm⁻¹ using a Fourier transform spectrometer. A new electronic assignment of ⁴Γ–X⁴Φ has been proposed. Rotational analysis has been obtained for the 0–0 and 1–1 vibrational bands of the ⁴Γ_5/2–X⁴Φ_3/2, ⁴Γ_9/2–X⁴Φ_7/2, and ⁴Γ_11/2–X⁴Φ_9/2 subbands and the 0–0 band of ⁴Γ_7/2–X⁴Φ_5/2. The lower state rotational and centrifugal distortion constants are consistent with the previous results [J. Mol. Spectrosc. 184 (1997) 186; J. Chem. Phys. 119 (2003) 9496], to the conformation that the lower state of the 407 nm band is the ⁴Φ ground electronic state. Rough estimates of the vibrational interval ΔG(1/2) and the spin–orbit coupling constant A in the ⁴Γ state were also obtained.     

Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Ultrabroadband single-pulse CARS of liquids using a spatially dispersive Stokes beam

A double-channel spectrometer, which enables to acquire ultrabroadband single-pulse spectra of liquids by Coherent Anti-Stokes Raman Spectroscopy (CARS), is described. The method used to fulfill the phase-matching condition is based on the fact that the CARS efficiency in dispersive media is the largest when the interactive waves cross each other under frequency-determined angles. The dependence of the spatial separation between the pump and Stokes beam, in front of the crossing CARS lens, due to their frequency difference is analysed. It is shown that the different spectral components of an ultrabroadband Stokes source have phase-matched the CARS process when they are laterally shifted by a conjugated prism pair and focused into the sample. The method is tested in the spectral region 2800–3800 cm^–1 of a non-resonant medium (CCl₄) using an ultrabroadband dye laser (1000 cm^–1 FWHM). The influence of the Stokes beam spatial dispersion on the width of CARS generation is demonstrated. By this method, 1060 cm^–1 wide single-pulse spectra of the OH stretching vibration of liquid water are obtained for the first time. The ratio between the resonant and non-resonant part of the third-order susceptibility in water and methanol is determined.     

New observation of the , 1Δg, and 2Πg states and molecular constants with all Li2, Li2, and LiLi data

This paper reports our new observation of the , 1³Δ_g (v = 2–4), and 2³Π_g (v = 2–8) states of ⁶Li⁷Li by continuous wave perturbation facilitated optical–optical double resonance spectroscopy. Combining our new experimental term values of ⁶Li⁷Li with the available experimental data of ⁶Li₂ and ⁷Li₂, molecular constants and potential energy curves by Rydberg–Klein–Rees and direct-potential-fit techniques have been determined. Born-Oppenheimer breakdown parameters of the Li₂ 1³Δ_g and 2³Π_g states are calculated.     

Reaction of the muonium substituted cyclohexadienyl radical with 2,3-dimethyl-1,3,-butadiene

The rate constant for the title reaction is represented by log (k _M/M^–1s^–1)=6.9(4)–700(350)K/T between 279 and 343K, whereas the H analogous radical, C₆H₇, reacts at room temperature withk _H 12 M^–1s^–1 with dimethylbutadiene. The title reaction is proposed to be transfer of the light hydrogen isotope, Mu, and the large kinetic isotope effect is discussed.Support by the Swiss National Foundation for Scientific Research and by the Swiss Institute for Nuclear Research (SIN) are gratefully acknowledged.     

A polarized CARS investigation of the fine structure population inversion of Cl atoms from laser photolysis of ICl and the quenching of Cl(2 P 1/2) by O2

The time resolved polarized CARS technique has been used to detect Cl atoms produced by photolysis of ICl in the presence and absence of O₂. A population inversion was observed between the ground state electronic levels Cl(² P _1/2) and Cl(² P _3/2). The rate constant for Cl(² P _1/2) decay (quenching + reaction) in ICl was determined to be (3.2±0.2)×10^–13 cm³/molecule×s; the rate constant for Cl(² P _3/2) reaction with ICl was determined to be (7.8±0.5)×10^–12 cm³/molecule×s; and the rate constant for Cl(² P _1/2) quenching by O₂ was determined to be (1.9±0.2)×10^–13 cm³/molecule×s.     

The AΠu state of : Electric properties, fine and hyperfine coupling constants, and magnetic moments (g-factors). A theoretical study

Several properties are calculated for A²Π_u of —the majority for the first time—including electric and magnetic moments, and fine/hyperfine structure (fs/hfs) parameters. The new results are compared with our previous ones for X² and B² of [P.J. Bruna, F. Grein, J. Mol. Spectrosc. 227 (2004) 67–80]. The electric quadrupole Θ and hexadecapole Φ moments, polarizability α, and hfs constants a, b, c, d, eQq₀, eQq₂ are evaluated at the density functional theory (DFT) level [B3LYP/aug-cc-pVQZ]. The fs constants (spin–orbit coupling A_Π, Λ-doubling p, q, spin-rotation γ_Π), and magnetic moments (g-factors) are obtained via 2nd-order sum-over-states expansions, using wavefunctions and matrix elements obtained with a multireference configuration interaction (MRDCI) method, and the Breit–Pauli Hamiltonian. At equilibrium, 2nd-order properties of A²Π_u are dominated by its coupling with B². For the A state, two independent components are reported for traceless tensor properties (multipoles Θ and Φ; hfs parameters c/d and q₀/q₂) and three for traced properties (polarizability α and g-factors), i.e., one more component than for axially symmetric Σ states. The currently available experimental data on — limited to A_Π, p, and q—are well reproduced by our theoretical results.     

Enhancement of upconversion luminescence in Tm/Er/Yb-codoped glass ceramic containing LiYF4 nanocrystals

A transparent Er³⁺–Tm³⁺–Yb³⁺ tri-doped oxyfluoride glass ceramics containing LiYF₄ nanocrystals were prepared. Under 980 nm laser diode (LD) pumping, intensive red, green and blue upconversion (UC) was obtained. The blue, green, and red UC radiations correspond to the transitions ¹G₄→³H₆ of Tm³⁺, ²H_11/2/⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2 of Er³⁺ ions, respectively. This is similar to that in Tm³⁺–Yb³⁺ and/or Er³⁺–Yb³⁺ co-doped glass ceramics. However, the blue UC radiations of the Er³⁺–Yb³⁺ co-doped glass ceramics is two-photon process due to cooperative energy transfer. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

Visible laser spectroscopy of cobalt monofluoride

The laser-induced fluorescence excitation spectrum of jet-cooled CoF molecules has been studied in the range of 18 800–22 000 cm⁻¹. Ten observed vibronic bands have been classified into three transitions with the 0–0 band at 18 909, 19 236, and 20 654 cm⁻¹, assigned as the [18.8]³Φ₄–X³Φ₄, [19.2]³Φ₄–X³Φ₄, and [20.6]³Γ₅–X³Φ₄ transition, respectively, the two ³Φ states, [18.8]³Φ and [19.2]³Φ, are consistent with Adam’s results (10). The previously unanalyzed [20.6] state is identified in the current work. A rotational analysis of [20.6]³Γ₅–X³Φ₄ transition has been performed and effective equilibrium molecular constants have been determined for the first time. In addition, lifetime measurements of the three electronic transitions were carried out under the collision-free condition. From the lifetime analysis, we consider that the V=1, 2, and 3 vibrational levels of [18.8]³Φ state are perturbed by another state.     

Oxygen nonstoichiometry of Sr(Co,Fe)O3−δ-based perovskites: I. Coulometric titration of SrCo0.85Fe0.10Cr0.05O3−δ by the two-electrode technique

The p(O₂)–T–δ diagram of perovskite-type SrCo_0.85Fe_0.10Cr_0.05O_3−δ was determined by the coulometric titration technique in the temperature range 770–1250 K at oxygen partial pressures from 8 10⁻¹⁰ to 0.5 atm. Stability of the cubic perovskite phase of SrCo_0.85Fe_0.10Cr_0.05O_3−δ, existing down to the oxygen pressures of 10⁻³–10⁻⁵ atm, was found to be slightly higher than that of SrCo_0.80Fe_0.20O_3−δ, probably due to stabilization of oxygen octahedra neighboring Cr⁴⁺ cations. When the oxygen nonstoichiometry of the Cr-containing perovskite decreases from 0.47 to 0.38, the partial molar enthalpy and entropy for overall oxygen incorporation reaction vary in the ranges −165 to −60 kJ mol⁻¹ and 90 to 150 J mol⁻¹ K⁻¹, respectively. Within the stability limits of the single perovskite phase, the p(O₂)–T–δ diagram can be adequately described by equilibrium processes of oxygen incorporation, cobalt disproportionation and interaction of cobalt and iron cations, with the thermodynamic functions independent of defect concentrations. Increasing grain size in SrCo_0.85Fe_0.10Cr_0.05O_3−δ ceramics from submicron size to 100–200 μm has no effect on the oxygen thermodynamics. The two-electrode coulometric titration technique, based on the alternate use of electrodes for oxygen pumping and e.m.f. measurements, is described and verified by studying oxygen nonstoichiometry of La_0.3Sr_0.7CoO_3−δ and PrO_x.     

Temperature measurement by single-shot dual-line CARS in low-pressure flows

A CARS method, adapted for diagnostics in low-pressure unsteady flows is described. The technique employs two narrow-band dye lasers and a single-frequency pump laser. Single-shot rotational temperature is obtained from the ratio of the intensities of two isolated Q lines. Temperature-measurement accuracy is discussed. The advantage of referencing the CARS signals from the flow in a cell filled with the same gas is shown. Demonstrative experiments are performed using N₂ at pressures of 10²–10³ Pa.     

Density, viscosity, and excess properties of the binary mixture of diethylene glycol monomethyl ether + water at T = (293.15, 303.15, 313.15, 323.15, 333.15) K under atmospheric pressure

Densities and viscosities have been measured as a function of composition for the binary liquid mixture of diethylene glycol monomethyl ether CH₃O(CH₂)₂O(CH₂)₂OH + water at T = (293.15, 303.15, 313.15, 323.15, 333.15) K under atmospheric pressure. Densities were determined using a capillary pycnometer. Viscosities were measured with Ubbelohde capillary viscometer. From the experimental data, the excess molar volumes V^E, and viscosity deviations δη, and the excess energies of activation for viscous flow ΔG^*E were calculated. These data have been correlated by the Redlich–Kister type equations to obtain their coefficients and standard deviations. The results suggest that molecular interaction between diethylene glycol monomethyl ether and water is strong.     

Tandem diazonium salt electroreduction and click chemistry as a novel, efficient route for grafting macromolecules to gold surface

Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N₃) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N₃ substrate was obtained by nucleophilic attack of NaN₃ on gold substrates modified by the electrochemical reduction of the , ⁺N₂–C₆H₄–CH₂Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C₆H₄–CH₂Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N₃ by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF₂)₇- chain and terminal CF₃. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N₃ to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm⁻¹); CF₂ (1000–1100 cm⁻¹) and CF₃ (1100–1350 cm⁻¹) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.     

Reinvestigation of the (4, 20) band of the O2 second negative system

High resolution absorption spectra of the (4, 20) band in the second negative system (A²Π_u–X²Π_g) of O₂⁺ cation were measured and analyzed in the range of 11 900–12 300 cm^–1 via optical heterodyne velocity modulation spectroscopy. Precise molecular constants of the levels involved were obtained by a nonlinear least-squares fitting procedure combining with our previous spectra of the (4, 19) and (6, 20) bands.     

Ion–ion interactions of LiPF6 and LiBF4 in propylene carbonate solutions

Self-diffusion coefficients of Li⁺ D_Li⁺, PF₆⁻ D_PF6⁻ and solvent propylene carbonate (PC) D_PC in LiPF₆−PC solutions were determined at 298 K by the pulse gradient spin echo (PGSE) NMR technique over the salt concentration range of 0.1–3.0 M (M = mol dm^– 3). The order of the diffusion coefficients was found to be D_Li⁺ < D_PF6⁻ < D_PC over the concentration range examined, and they were monotonically decreased with increasing the salt concentration. Haven ratio Λ/Λ_NMR, where Λ and Λ_NMR represent the ionic conductivity measured electrochemically and that estimated via the Nernst-Einstein equation using the diffusion coefficient, respectively, was evaluated as the measure of the ion–ion interaction in the LiPF₆–PC solutions. Though Λ/Λ_NMR values for LiPF₆-solutions decrease with increasing the salt concentration, they were greater than those for LiBF₄–PC solutions over the whole concentration range examined, which indicates that the ion pair formation ability of PF₆^– ion is weaker than that of the BF₄^– ion. The smaller value of the ionic conductivity for the highly concentrated LiPF₆–PC solution (above 2.0 M) than that of the LiBF₄-solutions can be attributed to the more rapidly increased viscosity relative to the LiBF₄-solution. Classic molecular dynamics (MD) simulations for the respective LiPF₆ and LiBF₄-solution of 0.5 and 1.0 M were also carried out based on the effective pair potentials. Diffusion coefficients, ionic conductivity and Haven ratio for these solutions were calculated from MD trajectories, and they qualitatively agree with those evaluated by experiments. Pair correlation functions g_LiO(r) (for Li⁺–O (PC) pair) and g_LiPF6(r) (for Li⁺–PF₆^– pair) or g_LiBF4(r) (for Li⁺–BF₄^– pair) revealed that the lithium ion weakly forms the contact ion pairs with PF₆^–, whilst strongly with BF₄^–, which supports the present experimental results. Moreover, the simulation results show that both anions in the contact ion pairs predominantly take the monodentate form, which is in contrast to the multidentate coordination predicted by ab initio calculation in gas phase.