The ν4 and ν2 Raman bands of CHD3

The CHD₃ Raman spectrum from 1925 to 2455 cm^?1 has been photographed with a resolution of about 0.2 cm^?1, showing the overlapping ν₂ and ν₄ bands. Ground state combination differences yield C₀ = 2.6297 ± 0.0003 cm^?1. The ν₄ state is weakly perturbed, but reasonably accurate values could be obtained for ν₄ = 2250.88 ± 0.10 cm^?1, (Cζ)₄ = 0.656 ± 0.010 cm^?1, C₄ - C₀ and B₄ - B₀. Some of these constants differ significantly from values previously estimated by infrared workers. For the ν₂ state the constants determined are in good agreement with recent infrared results.     

Electron paramagnetic resonance of Dy3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Dy³⁺ ions in lead thiogallate PbGa₂S₄ single crystals have been presented. It has been shown that the ground state of these ions corresponds to the lowest Stark sublevel Γ₆ of the term ⁶ H _15/2. The spectra are well described by the axially symmetric spin Hamiltonian with the effective spin S = 1/2 with the factors g _‖ = 15.06 and g _⊥ = 2.47. The Dy³⁺ ions substitute Pb²⁺ ions in the crystal lattice of PbGa₂S₄. The observed hyperfine structure has allowed to unambiguously interpret the EPR spectra. The hyperfine interaction constants of two odd isotopes of dysprosium in lead thiogallate single crystals have been found to be A _‖ = 675 × 10^?4 cm^?1 and A _⊥ = 111 × 10^?4 cm^?1 for ¹⁶³Dy and A _‖ = 472 × 10^?4 cm^?1 and A _⊥ = 77 × 10^?4 cm^?1 for ¹⁶¹Dy.     

Electronic photodissociation spectra of the Arn-C4H2 (n=1-4) weakly bound cationic complexes

Electronic spectra of a series of weakly bound clusters consisting of argon (Ar_n, n=1-4) bound to the butadiyne cation, C₄H₂⁺, have been recorded in the visible range from 440 to 520 nm by photodissociation. The C₄H₂⁺ fragment signal was recorded as a function of the laser wavelength during excitation of the A←X electronic transition. The observed transitions were assigned to the band origin of the cationic complexes and to vibronic bands involving excitation of the ν₃ and ν₇ vibrational modes of the C₄H₂⁺ moiety, as well as combination bands of these modes. Comparison of the photodissociation spectra of the various clusters reveals a small blue shift, 25 cm⁻¹ of the band maxima relative to the corresponding transitions reported from gas phase spectra of the bare C₄H₂⁺ cation. The magnitude of the blue shift of each band increases with successive Ar solvation up to n=3. Furthermore, each band becomes increasingly broadened towards the red with the addition of Ar atoms due to an increasing number of unresolved transitions involving excited intermolecular modes.     

Absorption spectrum of Cs2Mg(SO4)2 · 6H2O:Ni2+ single crystals

The absorption spectrum of Ni²⁺ doped in Cs₂Mg(SO₄)₂ · 6H₂O single crystals has been studied at room and liquid nitrogen temperatures in the range 7000–34000 cm^?1. The observed spectrum is satisfactorily interpreted in terms of cubic ligand field model including spin-orbit coulping. The ligand field parameters evaluated to best fit the observed spectrum are B = 955 cm^?1, C = 3572 cm^?1, Dq = 910 cm^?1 and ξ = 550 cm^?1. The non-ligand field band observed at 77K has been interpreted to be the superposition of vabrational mode of SO₄^2? radical on ₃T_1g(F) band.     

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.     

Supertransferred hyperfine structure in EPR of V4+ ion in Ca3In2Ge3O12 garnet

Interaction of an unpaired electron of the tetrahedral V⁴⁺ ion in Ca₃In₂Ge₃O₁₂ garnet with the four nearest In nuclei gives rise to clearly resolved structure of EPR spectra. We report the observation and analysis of these spectra at three frequencies and at temperature 77 K. The temperature dependence between liquid helium and the room temperatures was also studied. Parameters of the spin Hamiltonian are g_∥=1·8735; g_⊥=1·9825; ∣ ¦A∥|=150·4×10^?4cm^?1; ¦ A_⊥¦ = 36·7 × 10^?4 cm^?1. The supertransferred hyperfine interaction was found to be isotropic, absolute value of the corresponding parameter a is 22·1 × 10^?4 cm^?1.     

Mößbauereffekt in FeCl2, FeSO4 und FeSO4 · 7 H2O

Mößbauereffect measurements were performed with FeCl₂, FeSO₄ and FeSO₄ · 7 H₂O in the temperature range between 5 and 300 ?K. The quadrupole splittings at 5 ?K were determined to be (1.300±0.027) mm/sec, (3.650±0.053) mm/sec, and (3.350±0.053) mm/sec respectively. From the temperature dependence of the quadrupole splittings it follows that in FeCl₂ the energy of the excited 3d-electron-level isδ=150 cm^?1, in FeSO₄ δ ₁=360 cm^?1 andδ ₂=1680 cm^?1 and in FeSO₄ · 7 H₂Oδ ₁=480 cm^?1 andδ ₂=1300 cm^?1. The magnitudes of the magnetic field at the iron nucleus at 5 ?K are (202±8) kOe for FeSO₄ and (0±4) kOe for FeCl₂.     

Absorption spectra of diatomic molybdenum nitride (MoN), molybdenum oxide (MoO), and molybdenum dimer (Mo2) molecules isolated in Ar,Ne, and Kr matrices

MoN and MoO molecules produced in a hollow cathode discharge have been trapped in Ne, Ar, and Kr matrices at 4.2 and 13 K and investigated by optical spectroscopy. Bands attributed to MoN were identified in the red and blue spectral regions and assigned by comparison with gas phase results to the A⁴π → X⁴Σ^? (a) and B⁴Σ → X⁴Σ^? (a) transitions, respectively. The ground state of Mo¹⁴N has been identified as ⁴Σ^? with ω_e = 1040 cm^?1 in an Ar matrix. Absorptions assigned to MoO in the red spectral region form the (0-0) and (1-0) bands of at least one electronic transition, but could not definitely be correlated with the gas phase results. The ground state vibrational frequency for Mo¹⁶O in an Ar matrix is 893.5 cm^?1. Additionally, Mo₂ absorptions centered at 19 305 cm^?1 were shown to be part of a vibrational progression with an average spacing of 181 cm^?1.     

Mößbauereffekt in Eisenstilben und FeCl2·H2O

Using Mößbauer effect measurements in the temperature range between 3 °K and 310 °K the magnetic fields at the nucleus in iron-stilbene, FeCl₂·H₂O and FeCl₃ are determined to beH _T=0=(250±10) kOe, (252±18) kOe and (468±10) kOe; a Néel-temperature ofT _N=(23±1) °K is measured for iron-stilbene. The electric quadrupole splittings atT=0 °K for iron-stilbene and FeCl₂ ·H ₂ O, ΔE=(+2.52±0.02) mm/sec and (+2.50±0.05) mm/sec, yield electric field gradients at the iron nucleus ofq _z=+9.7·10¹⁷ V/cm² and +9.6·10¹⁷ V/cm², whereq _z⊥H; Debyetemperatures of θ=162 °K and 188 °K are obtained. The energy of the excited 3d-electron levels in iron-stilbene is estimated to Δ₁=309 cm^?1 and Δ₂=618cm^?1 as deduced from the temperature dependence ofΔE. In contrast to the suggestion ofEuler andWillstaedt bivalence of the iron in ironstilbene is found; its composition is shown to be 4(FeCl₂ ·H ₂O)·stilbene.     

Analysis of the ν6(A″2) band of cyclopropane-d6 recorded under high resolution

The parallel band ν₆(A″₂) of C₃D₆ near 2336 cm^?1 has been studied with high resolution (Δν = 0.020 – 0.024 cm^?1) in the infrared. The band has been analyzed using standard techniques and the following parameters have been determined: B″ = 0.461388(20) cm^?1, D″_J = 3.83(17) × 10^?7 cm^?1, ν₀ = 2336.764(2) cm^?1, α^B = (B″ ? B′) = 8.823(12) × 10^?4 cm^?1, β^J = (D″_J ? D′_J) = 0, and α^C = (C″ ? C′) = 4.5(5) × 10^?4 cm^?1.     

Infrared spectrum of formaldehyde: Coriolis interactions in the combination bands ν2 + ν6 and ν2 + ν3

A high-resolution infrared spectrum of H₂CO was measured in the range from 2600 to 3300 cm^?1. Vibration-rotation lines assigned to the combination bands ν₂ + ν₃ (a-type) and ν₂ + ν₆ (b-type) were analyzed as asymmetric-rotor bands by taking account of the Coriolis interactions among the ν₂ + ν₃, ν₂ + ν₆, and ν₂ + ν₄ states, though none of the ν₂ + ν₄ band lines have yet been definitely identified. The main results in cm^?1 units (with 2.5 times standard errors in the last digits given in parentheses) are: ν₀ = 3238.45(1), A - B?= 8.252(3), B?= 1.2053(2), and B - C = 0.1719 (assumed) for ν₂ + ν₃; ν₀ = 3000.10(1), A - B?= 8.125(46), B?= 1.2075(5), and B - C = 0.1693(14) for ν₂ + ν₆; and ν₀ = 2904.6(48), A - B?= 8.225(54), B?= 1.2023(20), and B - C = 0.1522 (assumed) for ν₂ + ν₄; the effective Coriolis interaction terms are: ξ_26,24^a = 10.10(3)cm^?1 and ξ_23,26^c = 0.96(3)cm^?1 under the assumption that ξ_23,24^b = 1.2841cm^?1. A second combination band 2ν₂ + ν₆ measured with lower resolution gave ν₀ = 4734.81(6)cm^?1.     

An experimental study of the collisional broadening of the Na-D lines by Ar and N2 perturbers in flames and vapor cells—II. The line wings

In this paper, we report on measurements of the fluorescence-excitation profile of the red Na-D₁ line wing from about 1 cm^?1 to 1100 cm^?1 and of the blue Na-D₂ line-wing from about 1 cm^?1 to 600 cm^?1, with respect to the corresponding line centre. We have also measured the fluorescence-excitation profile of the red Na-D₂ and blue Na-D₁ inner (overlapping) line wings from 1 cm^?1 with respect to the centre of each of the lines. All these wings were measured in several premixed, laminar, shielded H₂O₂Ar and H₂O₂N₂ flames at 1 atm (1400 K ? T ? 2300 K). We also measured these wings in a vapor cell containing Ar or N₂ perturbers (T ～ 480 K, p ～ 0.4 atm) in order to determine the influence of temperature on these wings. Using a tunable CW dye laser as excitation source, we determined the fluorescence-excitation profiles by measuring the total fluorescence intensity while tuning the laser wavelength. In order to specify the contributions that the different kinds of major flame perturbers (Ar, N₂, H₂O) make to the wings, we compared the wing profiles measured in various flames of different flame-gas compositions. In this comparison, the wing profiles were normalized with respect to the line-centre. We compared our measurements of far red Na-D₁ and blue Na-D₂ line-wings ($\text{Δσ ? 30}\text{cm}{}^{\mathrm{?1}}$) specified to Ar perturbers (at T = 500 K and T = 2000 K) with the results derived from quasi-static theory using available interaction potential data. In the case of Ar perturbers at T = 500 K, we observed a satellite at about 8 cm^?1 from the line-centre on the red Na-D₁ wing: this satellite was absent at T = 2000 K. The position of this red satellite was explained with the help of a set of “modified” potentials, which were constructed for interpreting the collisional Na-D broadening- and shift-rates deduced from our line-core observations and which were reported in Part I of this paper.     

The ground state of molecular hydrogen

The v = 0?0 quadrupole spectrum of H₂ has been recorded using a 0.005-cm^?1 resolution Fourier transform spectrometer. The rotational lines S(1) through S(5) are observable in the spectra, in the region 587 to 1447 cm^?1. The spectral position for S(0) was also obtained from its v = 1-0 ground-state combination difference. The high accuracy of the H₂ measurements has permitted a determination of four rotational constants. These are (in cm^?1) B₀ = 59.33455(6); D₀ = 0.045682(4); H₀ = 4.854(12) × 10^?5; L₀ = ?5.41(12) × 10^?8. The hydrogen line positions will facilitate studies of structure and dynamics in astrophysical objects exhibiting infrared H₂ spectra. The absolute accuracy of frequency calibration over wide spectral ranges was verified using 10-μm CO₂ and 3.39-μm CH₄ laser frequencies. Standard frequencies for 5-μm CO were found to be high by 12 MHz (3.9 × 10^?4 cm^?1).     

Tunable diode laser measurements of N2- and air-broadened halfwidths: Lines in the (ν4 + ν5)0 band of 12C2H2 near 7.4 μm

Nitrogen- and air-broadened Lorentz halfwidths have been determined for 29 lines in the P and R branches of the (ν₄ + ν₅)⁰ combination band of ¹²C₂H₂ using a tunable diode laser spectrometer. Two tunable diode lasers operating in the region 1250–1380 cm^?1 were used in recording the data. For nitrogen broadening, the measured halfwidths at 296 K decrease from about 0.11 cm^?1 atm^?1 at |m| = 1 to about 0.05 cm^?1 atm^?1 at |m| = 30, where m = J″ + 1 for R-branch lines, m = ?J″ for P-branch lines, and J″ is the lower state rotational quantum number. On the average, the air-broadened halfwidths are 97% of the N₂-broadened halfwidths.     

The infrared spectrum of C3O2: The interaction between ν7 and the ν2 and ν4 vibrations

The 3ν¹₇, 3ν³₇, and 4ν⁰₇ hot bands of the ν₄ fundamental of C₃O₂ in the 1580 cm^?1 region were analyzed from tunable diode laser spectra and the ground state to ν₄ + 2ν⁰₇ band at 1644 cm^?1 from Fourier transform spectra (FTS). The molecular constants for all of the v₄ 1 ← 0 bands as well as the intensity of the ν₀ + 2ν⁰₇ sum band relative to the ν₄ fundamental were in agreement with the predictions of the model of Weber and Ford. FTS spectra at 0.05 cm^?1 resolution were obtained of the sum and difference bands of ν₂ with ν₇ in the 750–900 cm^?1 region. Sharp Q branches occur for each ν₇ state in the sum bands, but only a number of R-branch bandheads and no recognizable Q branches in the difference bands. Assignments of the sum band Q branches through v₇ = 6 were made and molecular constants were determined for the ν₂ + ν¹₇ ← 0 transition at 819.7 cm^?1. The ν₇ potential function in the v₂ = 1 state was found to have a 1.2 cm^?1 barrier with a minimum at α = 4.9°, where 2α is the angular deviation from linearity. The Q-branch positions predicted from the calculated energy levels fit those observed within several cm^?1.     

Infrared rotation-vibration spectra of ethane: The perpendicular band, ν7, of C2H6

The study of the gas-phase infrared spectrum of C₂H₆ in the region of the perpendicular CH-stretching band, ν₇, near 3000 cm^?1 is extended for the ΔK = + 1 subbands as far as K = 20. The spectral resolution of ～0.030 cm^?1 is increased to ～0.015 cm^?1 by deconvolution. The earlier investigation of this band for KΔK = +9 to ?5, is repeated with greater accuracy, providing more reliable ground-state constants (cm^?1): B₀ = 0.663089 ± 24, D₀^J = (0.108 ± 4) × 10^?5, D₀^JK = (0.50 ± 7) × 10^?5. The molecular constants (cm^?1) for the ν₇ fundamental are B₇ = 0.66310 ± 3, A₇ = 2.682, ν₀ = 2985.39, ζ₇ = 0.128. A discussion of resonance effects in this band, in particular x-y-Coriolis and Fermi resonance, is given.     

Inverse Raman spectrum of the ν1-fundamental of CF4

We have obtained fully resolved spectra of the ν₁ (Q-branch) band of CF₄ at a pressure of 4 Torr using a variation of stimulated Raman spectroscopy. With an experimental resolution of ≤0.004 cm^?1, no detectable tensor splitting of the rotational levels exists up to J = 55. The spectrum is readily fit with a band origin α = 909.0720 cm^?1 and a single rotational term β ? β₀ = ?3.417 × 10^?1cm^?1. We have also observed an underlying hot band, which we tentatively assign as the ν₁ + ν₂ ← ν₂ transition, with α′ = 909.1997 cm^?1 and (β ? β₀)′ = ?3.405 × 10^?4cm^?1.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

The ground-state rotational constants of germane

The ground-state rotational constants B₀, D₀, and H₀ have been determined for GeH₄ from the analysis of ground-state combination differences in the infrared spectra of isotopically enriched ⁷⁰GeH₄, ⁷²GeH₄, and ⁷⁴GeH₄. The spectra were recorded at 0.06-cm^?1 resolution and about 0.005-cm^?1 precision for unblended lines. Suitable combination differences were found in both the ν₂ and the ν₄ infrared bands. The ground-state constants were assumed to be invariant to isotopic substitution at Ge, and the tensor distortion constants were held fixed at their microwave values. The results obtained are: B₀ = 2.69587 ± 0.00007 cm^?1, D₀ = (3.34 ± 0.03) × 10^?5 cm^?1, H₀ = (1.3 ± 0.5) × 10^?9 cm^?1.     

The infrared spectrum of OH-compensated defect sites in C-doped MgO and CaO single crystals

The IR spectra of OH-compensated point defects in MgO (and CaO) single crystals of various purity grades were reinvestigated. Three distinct groups of IR bands appear in the O-H stretching region: A, B and C around 3550 cm^?1 (3650 cm^?1), 3300 cm^?1 (3450 cm^?1) and 3700cm^?1 (3750cm^?1). They are assigned as follows: band A to the fully compensated, band B to the half compensated and band C to the overcompensated cation vacancies, [O?V”_catH?]^×, [O?V”_cat], and [O?O?V”_catH?$\text{]}\text{?}$, respectively.Upon cooling to 80 K the band A shows a complex behavior partly due to the formation of Ha molecules by charge transfer and concommittant O^? formation: [? (H₂)”_cat?]^×. The O^? represent defect electrons or positive holes in the O^2? matrix.Bands A and B show a characteristic multiplet splitting which is caused by local lattice strains coming from carbon atoms on near-by interstitial position. The intensity ratios between the multiplet components remain constant regardless of temperature pretreatments up to 1470 K, but strong variations of the integral intensities are observed. These are caused by the highly mobile C atoms entering and leaving reversibly the cation vacancy sites as a function of temperature and of the quenching speed. When the C atoms push the H₂ molecules onto interstitial sites, an H-H stretching signal appears around 4150cm^?1.