Oscillator strengths from line absorption in a high-temperature furnace—II. The (0,0) band of the B2σ+—X2σ+ transition in CN*

Quantitative high-resolution absorption spectroscopy was applied to the (0,0) violet band of CN. The CN radical was prepared in a furnace at 1421°K containing pure cyanogen gas. Since the calculated CN concentration is dependent on the controversial CN heat of formation, only the relationship, f_υ = 6·84 X 10^-3exp (0·354δ), where f_υ is the excess over the initially assumed ΔH⁰_f(CN) = 100·8 kcal/mole, could be directly determined in this study with an estimated error in f_υ of ±20%. For δ = 0, our f_υ is a factor of 4·8 smaller than an average value of 0·033±0· derived from other measurements. If this latter value of f_υ is assumed, our relationship yields ΔH⁰_f(CN) = 105·3±1· kcal/mole or D₀(CN) = 7·66±0·05 eV. The rotational temperature and line widths for this band were also measured.     

Investigation of the kinetics of OH∗ and CH∗ chemiluminescence in hydrocarbon oxidation behind reflected shock waves

The temporal variation of chemiluminescence emission from OH^?(A² Σ ⁺) and CH^?(A² Δ) in reacting Ar-diluted H₂/O₂/CH₄, C₂H₂/O₂ and C₂H₂/N₂O mixtures was studied in a shock tube for a wide temperature range at atmospheric pressures and various equivalence ratios. Time-resolved emission measurements were used to evaluate the relative importance of different reaction pathways. The main formation channel for OH^? in hydrocarbon combustion was studied with CH₄ as benchmark fuel. Three reaction pathways leading to CH^? were studied with C₂H₂ as fuel. Based on well-validated ground-state chemistry models from literature, sub-mechanisms for OH^? and CH^? were developed. For the main OH^?-forming reaction CH+O₂=OH^?+CO, a rate coefficient of k ₂=(8.0±2.6)×10¹⁰ cm³?mol^?1?s^?1 was determined. For CH^? formation, best agreement was achieved when incorporating reactions C₂+OH=CH^?+CO (k ₅=2.0×10¹⁴ cm³?mol^?1?s^?1) and C₂H+O=CH^?+CO (k ₆=3.6×10¹²exp(?10.9 kJ?mol^?1/RT) cm³?mol^?1?s^?1) and neglecting the C₂H+O₂=CH^?+CO₂ reaction.     

Optical characterization of fourfold (Td)- and sixfold (Oh)-transition-metal species in MgAl2O4:Co by time-resolved spectroscopy

This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl₂O₄:Co²⁺. Besides the well-known fourfold-coordinated Co²⁺(T_d) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr³⁺(O_h) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co²⁺(T_d) emission at 670 nm varies from τ=6.7 μs to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T_d systems is related to the excited-state crossover (⁴T₁↔²E), making the emission band to transform from a narrow-like emission from ²E at low temperature to a broad structureless band from ⁴T₁ at room temperature.     

Pulsed supersonic source of vdW complexes for high-temperature applications: Spectroscopy and beam characteristics

Application of a modified version of high-temperature high-pressure all-metal pulsed source of supersonic molecular beam is demonstrated in a production of van der Waals (vdW) complexes. The vdW complexes are produced possessing controllable rotational temperature (T _rot ) in the range from 3 K to 19 K. An effective control over T _rot is illustrated employing excitation spectrum recorded using the B ³1(5³ P ₁) ← X ¹0⁺(5¹ S ₀) transition in CdAr. First-time resolved rotational structure in the profile of the υ′ = 2←υ′′ = 0 vibrational component is reported. The control over T _rot is crucial in a dissociation of the (¹¹¹Cd)₂ isotopologue in the supersonic beam. For the process, excitation at well defined J′← J′′ rotational transition within the (υ′,υ′′) = (40,0) vibrational band of the A ¹0 _u ⁺(5¹ P ₁) ← X ¹0 _g ⁺(5¹ S ₀) transition is employed. It is followed by the dissociation using A ¹0 _u ⁺(υ′ = 40,J′′) → X ¹0 _g ⁺ bound → free transition. An analysis and simulation of the (40,0) vibrational band rotational structure are presented. Parameters describing conditions in the supersonic beam, degree of rotational cooling, Doppler broadening and spectral bandwidth of the laser beam are used.     

Variation of electronic transition moment with the internuclear separation for the (AO+−X1Σ+) band system of PbO

Relative integrated intensities of the (AO⁺?X¹Σ⁺) band system of PbO have been measured by photographic photometry. These have been interpreted with the aid of Franck-Condon factors (q_υ′υ″) and r-centroids ($\text{r}{}_{\mathrm{\upsilon \prime \upsilon ″}}$) to show that the variation of electronic transition moment with internuclear separation is R_e(r)=const.(0.521r?1). Arrays are shown for the band strengths S_υ′υ″.     

Structures of proton solvates in the HCl-H2O-(CH3)2NCHO system as determined by IR spectroscopy and quantum-chemical calculations

The structures of proton solvates in the HCl-H₂O-(CH₃)₂NCHO (DMFA) system at H₂O: DMFA ratios ranging from 1: 1 to 21: 1 are studied by the IR spectroscopy method. It is demonstrated that H₂O?H⁺?OH₂ ions and (CH₃)₂NCHO?H⁺?OH₂ mixed solvates with a strong quasi-symmetrical hydrogen bond are formed in solutions. With an increase in the DMFA concentration, the fraction of H₅O ₂ ⁺ ions decreases. At HCl: H₂O ≥ 1: 3 and arbitrary DMFA concentrations, only mixed proton solvates are formed. The continuous absorption coefficients for the (CH₃)₂NCHO?H⁺?OH₂ ions are determined. The results obtained are compared with the results of quantum-chemical calculations of the structure and relative stability of the (DMFA) _m H⁺(H₂O) _n (m = 0–2, n = 0–3) positively charged complexes which were performed by the B3LYP/6-31++G(d,p) DFT method. We identified 19 stable configurations with chain, cyclic, and branched structures. Most of these configurations contain the (CH₃)₂NCHO?H⁺?OH₂ fragment. The parameters of the O?H⁺?O bridge show that some configurations have a strong quasi-symmetrical hydrogen bond. In some cases, the proton is located between two DMFA molecules. The H₂O?H⁺?OH₂ bridge is observed in none of the stable configurations of the (DMFA) _m H⁺(H₂O) _n (m ≠ 0) complexes.     

L ∞ estimates for the space-homogeneous Boltzmann equation

This paper studies the boundedness of solutionsf of the initial-value problem for the space-homogeneous Boltzmann equation for inverse kth power forces, whenk>5, and under angular cutoff. The main result is that if the initial value isf ₀ ? 0 with (1 + ¦υ¦²)φ₀ εL ¹ and (1 + ¦υ¦)^s f ₀ε L^∞ for somes > 2, then (1 + ¦υ¦^s'f _tεL ^∞ fort>0 and ess_υ,t sup(1 + ¦υ¦)^s'f(υ, t,) < ∞ for anys′ ? s whens ? 5, and anys′ ? s ifs > 5.     

Rotational analysis of the c3Πu–b3Πg system of P2

The rotationally resolved spectra of the c³Π_u–b³Π_g system of P₂ in the 16620–17860 cm^?1 region is reanalyzed here to obtain more assignments of the rotational lines and more accurate molecular constants. Approximately 500 spectral lines were assigned to six subbands: the Ω=0, 1 and 2 components of the (2, 3) band, the Ω=0 and 2 components of the (1, 3) band and the Ω=2 component of the (1, 2) band. Because of perturbations in the c³Π_u (υ=2) state, the Λ-doubling in the ³Π₂–³Π₂ subband of the (2, 3) band was resolved. By the weighted nonlinear least-squares fitting using two types of effective Hamiltonians, more accurate molecular constants for the υ′=1 and 2 levels in the c³Π_u state and for the υ″=2 and 3 levels in the b³Π_g state of P₂ were derived.     

1+ state and effective g-factor

The effects of nuclear field r²(Y₂σ₁)_1υ on magnetic properties of single-particle states in odd-A nuclei (^208±1Pb) are considered. The coupling constant associated with this type of field is estimated by an argument that realtes it to the coupling constant for the field (γ₀σ₁)_1υ. The effects of including the r²(Y₂σ₁)_1υ field on the M1 moments and transitions are estimated.     

Laser-induced fluorescence of the CH molecule in a low-pressure flame

The laser-induced fluorescence from [A²Δ(υ′ = 0)→X²Π(υ″ = 0)] band of the CH radical was studied in a low-pressure (20 torr) methane-oxygen flame (φ = 1.06). A time-resolved fluorescence technique was used to measure the relative CH concentration profile and the quenching of the A²Δ excited state through the flame. The pressure dependence of the quenching was also measured and used to determine an effective quenching cross section of 6 Ų in the CH₄-O₂ flame. Analysis of the fluorescence spectra scanned at different delays after the laser excitation, according to a pseudo-three-level model, yields a rotational energy transfer (RET) rate in the A²Δ(υ′ = 0) electronic state which is a factor of four faster than the electronic quenching rate of 1.57 × 10⁷ sec^-1 in the flame at 2000 K.     

Spectroscopic properties of the rubidium and cesium aluminum double molybdate crystals

Infrared, Raman, electron absorption, excitation and emission spectra were measured for RbCr_xAl_1−x(MoO₄)₂ and CsCr_xAl_1−x(MoO₄)₂ crystals (x=0-2%) at the temperatures ranging from 7 to 300 K. A very rich vibronic structure of the emission band was explained and assigned to the respective vibrational modes. One Cr³⁺ center characterized by 2.35 ms lifetimes for rubidium derivative and 1.3 ms for cesium one at 7 K for the ²E→⁴A₂ transition was identified for both crystals. The local structure of the Cr³⁺ surrounding is discussed in terms of the spectroscopic results and the crystal field parameters are derived for both materials.     

The stretching fundamental bands ν1, ν2 and ν4 of HSiD3

The ν₁(A₁), Si-H stretching, ν₂(A₁) and ν₄(E), Si-D stretchings, fundamental bands of HSiD₃ have been recorded at an effective resolution of ca. 0.003 cm⁻¹ between 2080 and 2280 cm⁻¹ and between 1480 and 1720 cm⁻¹, respectively. Ro-vibrational transitions of the H²⁸SiD₃ isotopologue have been assigned in the two spectral ranges, about 700 belonging to ν₁, with J′ up to 25 and K up to 21, and about 1600 to the ν₂/ν₄ dyad, with J′ up to 24 and K′ up to 19. The spectra of all the bands evidence the existence of several perturbations. The transitions of ν₁ have been analyzed either neglecting or including in the model A₁/E Coriolis-type interactions with nearby dark states. The υ₂ = 1 and υ₄ = 1 states have been fitted simultaneously taking into account several ro-vibrational interactions between them and, in addition, with the υ₅ = 2, l = 0 component, and with few other close dark states. The standard deviation of the fit for both ν₁ and the ν₂/ν₄ dyad is, however, more than one order of magnitude larger than the estimated experimental precision and is independent on the adopted model.     

SERS investigation of interfacial water at a silver electrode in acetonitrile solutions

Surface-enhanced Raman scattering from a silver electrode in solution of 0.1 M LiClO₄ in acetonitrile has been analyzed as a function of applied potential. Three ν(O-H) bands associated with the interfacial water and two ν(O-H) bands associated with the OH⁻ ion species were observed depending on the electrode potential. The band at 3487 cm⁻¹ is favored at relatively positive potentials and assigned to H₂O molecules interacting with the electrode surface via the oxygen atoms. Another band at 3586 cm⁻¹ appears in a wider potential region and is assigned to the H₂O molecules with one or both of the hydrogen atoms facing the electrode surface. Additionally, evidence for the possible surface ion pair, Li⁺OH⁻, which is closely associated with H₂O molecules and the quasi-crystalline form of LiOH are also presented in this paper.     

Photoionization and photoelectron angular distribution for H2

Photoionization of H₂(¹Σ_g⁺) in a vibrational υ″ and rotational N″ state into H₂⁺(²Σ_g⁺) in a vibrational υ′ and rotational N′ state is studied theoretically. The differential cross section, after summing over the final states, is expressed in the well-known simple form of $\text{(}\text{σ}{}_{\mathrm{T}}\text{4π}\text{)[1 + βP}{}_2\text{(}\text{cos}\text{θ)]}$. Parallel expressions are obtained for H₂⁺ in a specific υ′ state (in terms of σ(υ′) and β(υ′)) and for H₂⁺ in a rotational fine level υ′N′ (in terms of σ(υ′N′) and β(υ′N′)). Asymmetry parameters β, β(υ′) and β υ′N′), which are expressed in terms of Racah and Clebsch-Gordan coefficients and electronic transition moments, can be reduced approximately to 2 lineary polarized light and to -1 for unpolarized light. Using single-center electronic wave functions and including partial eaves l = 1, 3, and 5, σ(υ′) and β(υ′) are computed as a function of υ′ at 584 Å. The computed σ(υ′) divided by the Frank-Condon overlap, in agreement with experimental results, increases monotonically with υ′; σ_T and β are computed in the incident photon energy range of 600–4000 Å and the results compare favorably with previous calculations.     

The use of electron impact dissociation and the photon-photon cascade technique to measure the lifetime of the B2Σ+ state of CN

The lifetime of the (B³Σ⁺_{υ= 0, 1} state of the CN radical has been measured by the photon-photon delayed coincidence technique, the CN radical being produced by electron impact dissociation of acetonitrile. This is the first lifetime measurement in a free radical by this method. The optical cascade in the band spectrum of CN used for the present measurement is H²Π_r - B²Σ⁺ - X²Σ⁺. The lifetime of the (B²Σ⁺)_{υ=0, 1} state in CN has been found to be 61.1 ± 7.6 ns.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

Luminescence properties of novel NaBa4(BO3)3:Ce, Eu phosphors

Novel Eu³⁺, Ce³⁺ activated NaBa₄(BO₃)₃ phosphors were synthesized by solid-state reactions. The excitation spectrum of NaBa₄(BO₃)₃:Ce³⁺ consists of an intense band peaking at 350 nm and a weak band in the higher energy side, and the emission spectrum exhibits a blue band with a maximum at about 420 nm. The Eu³⁺ emission in NaBa₄(BO₃)₃ consists of the transitions from ⁵D₀ to ⁷F_J, and the excitation spectrum consists of broad excitation band peaking at 270 nm and some intense narrow lines. The optimum doped concentration, the critical distance of the concentration quenching, and the fluorescence lifetime have also been investigated.     

The rotational spectra of the υ8 = υ9 = 1 and υ6 = υ7 = 1 interacting vibrational states of nitric acid (HNO3)

The analysis of the rotational spectrum of HNO₃ has been extended to include the υ₈ = υ₉ = 1 state at 1205.7 cm⁻¹ and the υ₆ = υ₇ = 1 state at 1223.4 cm⁻¹. Based on 78-519 GHz data, the assignments in the 8¹9¹ vibrational state have been significantly expanded from the previously reported microwave measurements [T.M. Goyette, F.C. De Lucia, J. Mol. Spectrosc. 139 (1990) 241-243]. A new microwave analysis is also reported for the 6¹7¹ vibrational state. A simultaneous analysis takes into account the localized ΔK_a = ±2 Fermi resonances between the vibrational states, describes the torsional splitting of 3.3 and 1.4 MHz for the 8¹9¹ and 6¹7¹ states respectively, and fits to experimental accuracy over 1500 rotational transition frequencies that extend up to J = 59. Infrared energy levels [A. Perrin, J.-M. Flaud, F. Keller, A. Goldman, R. D. Blatherwick, F. J. Murcray, C. P. Rinsland, J. Mol. Spectrosc. 194 (1999) 113-123] were also included in the analysis and fit to experimental accuracy. Measurement of strongly perturbed transitions in each vibrational state provide a determination of the band origin difference of 17.733184(17) cm⁻¹. The rotational constants agree well with those predicted by vibrational-rotational constants of the fundamental modes. Furthermore, the analysis will provide a very accurate simulation of the infrared spectrum of HNO₃ in the 8.3 μm region.     

OH impurities in co-doped LiNbO3:Cr :ZnO congruent crystals

Infrared optical absorption has been used to study OH⁻impurities into congruent co-doped LiNbO₃:Cr³⁺:ZnO crystals doped with different Zn²⁺ concentration. The OH⁻ IR absorption spectra present three bands that can be associated with different OH⁻ complex centres available in the lattice. For crystals with lower Zn²⁺ concentrations (<4.7%) only one IR absorption band centred at 2867 nm (3490 cm⁻¹) is reported which is associated with the OH⁻ unperturbed vibration. For crystals with higher Zn²⁺ concentrations (>4.7%), two new bands associated with OH⁻vibration in distortion environment are reported. These bands are centred at 2827 nm (3537 cm⁻¹) and 2847 nm (3512 cm⁻¹) and can be associated with OH⁻-Zn²⁺ and Cr³⁺(Li⁺)-OH⁻-Zn²⁺(Int.) complex centres, respectively. Electron paramagnetic resonance (EPR) has been used to identify the Cr³⁺ centres in the lattice of the doped LiNbO₃:ZnO crystals.