Vibrational energy transfer in CH2F2

Infrared fluorescence has been observed from the ν₁, ν₆, 2ν₉, ν₈ and ν₄ levels of CH₂F₂ following excitation by a 9.6 μ Q-switch CO₂ laser. All the observed states exhibit a single exponential decay rate of approximately 44 msec^?1 torr^?1. The rare gas dependence of this rate has also been measured and found to be up to 20 times slower than the rate for the pure gas. Measurements of the risetimes of the observed fluorescence signals yielded an upper limit of 5 μsec at 1 torr for the ν₁, ν₆ and ν₈ levels. The 2ν₉ and ν₄ risetimes were effectively instantaneous under the experimental conditions that prevailed. The relative magnitudes of the measured rate are discussed in terms of existing V-T/R theories and collisional energy transfer processes.     

Vibration-vibration energy transfer iln CH3F

Previous works have reported vibration-vibration and vibration-translation transfer rates in CH₃F and CH₃FX mixtures. In this letter we report the study of the fast VV transfer rate populating the 3ν₃, ν₁ and ν₄ states of CH₃F. Gaseous CH₃F was initially excited to the ν₃ state by a TEA CO₂ laser operating on the P(20 9.6 μ line and collisional pumping to the 3ν₃, ν₁ and ν₄ states was measured by monitoring the rise time of the fluorescence at 300 cm⁻¹. The rate constant was found to be 2.2 × 10⁵ sec⁻¹ torr⁻¹.     

Energy exchange processes in a low temperature N2CO transfer laser

A liquid-nitrogen-cooled, active-N₂-pumped CO laser has produced cw oscillation from ν = 2 → ν = 1 (4.8 μm) to ν = 35 → ν = 34 (8.0 μm). An analysis of the output spectrum gives the VT relaxation rate of CO (ν ≈30) by He at 150°K as 2 × 10³ sec⁻¹ torr⁻¹.     

The laser sensitized reaction SF26 + NO + O3

A pulsed CO₂ laser was used to irradiate a rapidly flowing mixture of NO, O₃, and SF₆. When the laser was tuned to an SF₆ absorption line, an increase in the visible NO^*₂ emission was observed. The laser-induced signal has two unusual features. First, the rise time is much longer than is observed when O₃ is excited directly, and, second, the signal decays to a value above the original baseline. The rise rate is attributed to VV energy transfer from SF²₆ to O₃, while the baseline shift is attributed to a temperature jump resulting from rapid non-resonant VV relaxation within the SF₆ molecule. Both the size of the T-jump and the fraction of vibrationally excited ozone molecules vary inversely with NO pressure.     

Reactive and non-reactive quenching of O(1D2) by COF2

Quenching of O(¹D₂) by COF₂ has been investigated by time-resolved resonance fluorescence monitoring of the product O(³P_J) following 248 nm pulsed laser photolysis of O₃. The rate constant for total removal of O(¹D₂) by COF₂ is (7.4 ± 1.2) × 10^?11 cm³ molecule^?1 s^?1. 71 ± 7% of the quenching interactions result in formation of O(³P^J).     

Fluorescence spectra of laser-excited YO molecules in a H2O2Ar flame

CW dye laser induced fluorescence emission and thermal emission spectra of YO-molecules in a 1 atm H₂O₂Ar flame of 2430 K were recorded simultaneously. Narrow band laser excitation was applied to four rotational lines in the (1, 1) Q-branch of the A²Π_{$\text{3}\text{2}$}→X²Σ⁺ transition and broadband excitation was applied to several separate Q-branches of the A²Π_{$\text{1}\text{2}$,$\text{3}\text{2}$}→X²Σ⁺ transitions. From the differences between the fluorescence emission spectra and thermal emission spectra, we conclude that collisional de-excitation of an excited vibronic level takes place by vibrational relaxation, decay to the electronic ground state and by intermultiplet transfer in order of increasing probability.     

Slow energy transfer between vibrational models of CH2Cl2, CD2Cl2, CH2ClBr and CH2Br2

Inefficient vibrational energy exchange between the lowest vibrational mode and the higher lying vibrational modes of CH₂Cl₂, CD₂Cl₂, CH₂ClBr and CH₂Br₂ was investigated by ultrasonic absorption experiments. Breathing sphere theory is used to interpret the data available for VV and VR, T transfer in methylene halides.     

The crystal structure of Ba2V2O7

Ba₂V₂O₇ is triclinic with a = 13.571(3), b = 7.320(2), c = 7.306(2) Å, α = 90.09(1), β = 99.48(1), β = 99.48(1), γ = 87.32(1)°, V = 7.15.1 ų, Z = 4, and space group $\text{P}\text{1}$. The crystal structure was solved by Patterson and Fourier methods and refined by full-matrix least-squares analysis to a R_w of 0.034 (R = 0.034) using 2484 reflections measured on a Syntex $\text{P}\text{1}$ automatic four-circle diffractometer. The structure has two unique divanadate groups that are repeated by the b and c lattice translations to form sheets of divanadate groups parallel to (100). These sheets are linked by four unique Ba atoms that lie between these sheets. Ba(1) and Ba(3) are coordinated by eight oxygens arranged in a distorted biaugmented triangular prism and a distorted cubic antiprism, respectively. Ba(2) is coordinated by 10 oxygens arranged in a distorted gyroelongated square dipyramid and Ba(4) is coordinated by nine oxygens arranged in a distorted triaugmented triangular prism. These coordination numbers are substantiated by a bond strength analysis of the structure, and the variation in 〈BaO〉 distances is compatible with the assigned cation and anion coordination numbers. Both divanadate groups are in the eclipsed configuraton with 〈VO(br)〉 bond lengths of 1.821(4) and 1.824(4) Å and VO(br)V angles of 125.6(3) and 123.7(3)°, respectively. Examination of the divanadate groups in a series of structures allows certain generalizations to be made. Longer 〈VO(br)〉 bond lengths are generally associated with smaller VO(br)V angles. When VO(br)V < 140°, the divanadate group is generally in an eclipsed configuration; when VO(br)V > 140°, the divanadate group is generally in a staggered configuration. Nontetrahedral cations with large coordination numbers require more oxygens with which to bond, and hence O(br) is more likely to be three coordinate, with the divanadate group in the eclipsed configuration. In the eclipsed configuration, decrease in VO(br)V promotes bonding between O(br) and nontetrahedral cations, and hence smaller nontetrahedral cations are generally associated with smaller VO(br)V angles.     

Two-photon ionization spectrum of the 1Lb ← S0 transition in toluene

The multiphoton ionization (MPI) spectrum of toluene arising from the ¹B₂ (¹L_b) valence state has been investigated. The state participates as a two-photon resonance. A total of nine excited state fundamentals have been characterized, including three non-totally symmetric vibrations. The toluene MPI spectrum shows a strong resemblance to the two-photon fluorescence excitation spectrum with the strongest transitions taking place to the origin and excited state modes ν₁(a₁), ν₁₂(a₁) and ν₁₄(b)₂). The intensities of the observed fundamentals are rationalized in terms of Franck-Condon and vibronic coupling effects. A major conclusion is, that the primary mechanism for the activity of ν₁₂ is vibronic coupling.     

Anomalous vibrational relaxation of a hot S*1 state of 3,4-benzpyrene in 2-methylpentane

Two anomalous emission bands in the fluorescence spectrum of 3,4-benzpyrene, dissolved in 2-methylpentane, have been studied as a function of temperature. These emissions originate from the second excited singlet state S₂, and from a vibrationally excited S₁ (S^*₁) respectively. From the temperature dependence of the relative yield and the decay time of the S^*₁ emission it can be concluded that the vibrational relaxation of this state is hampered. The rate constant for this relaxation process is smaller that 4 > 62;x 10⁷ sec^?1.     

Infrared study of some specificities of the dπpπ interaction in organogermanium compounds

The analysis is presented for the frequencies of stretching modes ν(GeH) in the IR spectra of organogermanium compounds R₂XGeH, RX₂GeH, RXYGeH, X₂YGeH and XYGeH₂ (where R is a substituent which does not make a d_πp_π bond with germanium, and X and Y are groups capable of d_πp_π interaction with germanium). It is shown that ν(GeH) in these compounds is dependent on both the I effect of R, X and Y, and the d_πp_π interaction in GeX and GeY bonds. If only one substituent capable of d_πp_π interaction with germanium is present, the value of such an effect is determined by itsσo_Rconstant. However, when germanium is bound to several substituents capable of d_πp_π interaction its magnitude depends on the effective charge at germanium which is determined by the inductive and mesomeric effects of X and Y. The data obtained are compared to the dependences observed in the IR spectra of similar organosilicon compounds.     

High-pressure Raman study of vibrational relaxation in N2O

The vibrational widths of the ν₁ and ν₃ Raman bands of N₂O were determined at pressures ranging from 8 bar to 2 kbar and temperatures varied from 25 to 150°C. The different dephasing theories including motional narrowing collisional models and resonant vibrational energy transfer theory were tested. A comparison of the theoretical predictions with the experimental data indicates the resonance VV transfer represents the dominant broadening mechanism. The observed frequency shifts between isotropic and anisotropic components of the bands were interpreted in terms of dipole-dipole interactions in dense N₂O.     

A shock tube study of vibrational relaxation in SO2, SO2Ar and SO2He

Vibrational relaxation times in SO₂, SO₃Ar (11%, 20% and 54% SO₂) and SO₂He (9.5% SO₂) were measured behind incident shock waves using the laser schlieren technique in the temperature ranges 550–1200 K, 700–2100 K and 700–1600 K respectively for the three systems. An analysis of the density gradient signals revealed a double exponential behaviour consistent with earlier studies. The fast relaxation rates were not quantitatively studied and the slow relaxation rates were found to fit the following equations:

where Pτ is the relaxation time in atm μs and T is in °K. The collision numbers corresponding to the slower rates were found to agree well with a recent theoretical calculation using SSH-Tanczos theory.     

Preparation of COF2 using CO2 and F2 in the electrochemical cell with PbSnF4 as a solid electrolyte

Tetragonal PbSnF₄ was prepared by precipitation method with Pb(NO₃)₂ and SnF₂ aqueous solutions. The product was characterized using X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XFS), and the other chemical analyses. Tetragonal PbSnF₄ exhibited the highest electric conductivity of 3.2 Sm⁻¹ at 473 K in air as a fluoride ion conductor. We have investigated the possibility of COF₂ formation using CO₂ and F₂ in an electrochemical cell with PbSnF₄ as a solid electrolyte. At same time, we tried to produce an electric power from an electrochemical cell. This CO₂/F₂ electrochemical cell was constructed with a tetragonal PbSnF₄ disk having Au electrodes. The electromotive force was about 0.9 V at room temperature for 0.1 MPa CO₂/(0.01 MPa F₂ + 0.09 MPa Ar). However, the short circuit current density was 0.24 A m⁻², which was quite small. This current density was so small that no fluorocarbon compound was detected after 3 h discharge using FT-IR.     

Kinetics of the reactions of isopropoxy radicals with NO,NO2, and O2

A fluorescence excitation spectrum of (CH₃)₂CHO (isopropoxy radical) is reported following photolysis of isopropyl nitrite at 355 nm. Rate constants for the reaction of isopropoxy with NO, NO₂, and O₂ have been measured as a function of pressure (1–50 Torr) and temperature (25–110°C) by monitoring isopropoxy radical concentrations using laser-induced fluorescence. We have obtained the following Arrhenius expressions for the reaction of isopropoxy with NO and O₂ respectively: (1.22±0.28)×10^?11 exp[(+0.62±0.14 kcal)/RT]cm²/s and (1.51±0.70)×10^?14 exp[(?0.39±0.28)kcal/RT]cm³/s where the uncertainties represent 2σ. The results with NO₂ are more complex, but indicate that reaction with NO₂ proceeds more rapidly than with NO contrary to previous reports. The pressure dependence of the thermal decomposition of the isopropoxy radical was studied at 104 and 133°C over a 300 Torr range using nitrogen as a buffer gas. The reaction is in the fall-off region over the entire range. Upper limits for the reaction of isopropoxy with acetaldehyde, isobutane, ethylene, and trimethyl ethylene are reported.We have performed the first LIF study of the isopropoxy radical. Arrhenius parameters were measured for the reaction of i-PrO with O₂, NO, NO₂, using direct radical measurement techniques. All reactions are in their high-pressure limits at a few Torr of pressure. The rate constant for the reactions of i-PrO with NO and NO₂ reactions exhibit a small negative activation energy. Studies of the i-PrO + NO₂ reaction produce data which indicate that O(³P) reacts rapidly with i-PrO. Unimolecular decomposition studies of i-PrO indicate that the reaction is in the fall-off region between 1 and 300 Torr of N₂ and the high-pressure limit is above 1 atmosphere of N₂.     

On the luminescence of titanium-doped lithium zirconate (Li2ZrO3)

The luminescence of Li₂ZrO₃Ti is described. The emission and excitation spectra are reported. The temperature dependence of the decay time is discussed and points to a complicated energy-level scheme. Further, the decay time of the luminescence of ZrO₂Ti has been measured. It appears to be very long (～1 msec).     

The system NiAl2O4Ni2SiO4 at high pressures and temperatures: Spinelloids with spinel-related structures

Phase relations in the system NiAl₂O₄Ni₂SiO₄ were studied in the pressure range 1.5 ～ 13.0 GPa and in the temperature range 800 ～ 1450°C. Two new phases, IV and V, were found in regions of pressure higher than 4 GPa. Phase V disproportionates into a mixture of Ni₂SiO₄-spinel, NiO, and Al₂O₃ at approximately 9.5 GPa and 1100°C. Phases III, IV, and V form a solid solution in some compositional range: phases IV and V have a composition around NiAl₂O₄·Ni₂SiO₄, whereas phase III spreads from NiAl₂O₄·Ni₂SiO₄ to the NiAl₂O₄-rich side. All the phases I ～ V are structurally considered to be spinel derivatives, “spinelloids,” with three kinds of tetrahedral groups; isolated tetrahedra TO₄, linked ones T₂O₇, and triply linked ones T₃O₁₀. The ratios of isolated tetrahedra to linked ones are large in the higher-pressure phases and small in the lower-pressure phases. The difference of compositional range of phase III from that of phases IV and V is possibly explained by the avoidance of linked tetrahedra such as O₃AlOAlO₃.     

Dissociation rate measurements in SO2 + Ar mixtures behind incident shock waves

Dissociation rates of SO₂ in SO₂ + Ar mixtures at 6%, 11%, 15% and 20% of SO₂ were measured behind incident shock waves over a temperature range 4000–6000 K at initial pressures 1.0 to 2.5 Torr. The recorded laser schlieren signals exhibited two exponentials, the faster one due to vibrational relaxation and the slower one due to dissociation. The initial dissociation rate was calculated from the value of the density gradient at the point of intersection of the two exponentials. A least-squares analysis of the experimental data yielded the following empirical relations: k_SO2Ar = 3.34 × 10¹⁵ exp(?107.6 kcal mole^?1/RT) cm³/mole s, k_SO2SO2 = 5.02 × 10¹⁴ exp(?66.6 kcal mole^?1 kcal mole^?1/RT) cm³/mole s.     

Infrared multiple-photon dissociation of N2H4 and CH3NH2 fluence dependence of the production of NH2

The multiple-photon dissociation of N₂H₄ and CH₃NH₂ by pulsed CO₂ laser light to produce NH₂(X?²B_I has been studied using the laser-induced fluorescence detection method. The relative NH₂ yield, represented by the fluorescence signal, has been measured as a function of the fluence from the threshold at about 0.1 J/cm² to about 100 J/cm², at different CO₂-laser lines and at pressures down to 10^?4 Torr.     

Molecular structures of (SiCl3)2CH2 and (SiCl3)2CCl2 as studied by electron diffraction

An electron diffraction analysis of the molecular structures of 1,1,1,3,3,3-hexachloro-1,3-disilapropane and octachloro-1,3-disilapropane has been carried out. Deviations from the staggered conformation are indicated. The data may be approximated by models with C₂ symmetry and a small tilt of the SiCl₃ groups. The main bond lengths (r_g) and bond angles obtained for (SiCl₃)₂ CH₂ are: SiCl, 202.7(4); SiC, 186.6(6); CH, 109.8(24) pm, ClSiCl, 107.9(1); SiCSi, 118.3(7)°; and for (SiCl₃)₂CCl₂: SiCl, 202.0(4); SiC, 190.2(9); CCl, 179.6(9) pm; ClSiCl, 109.5(1); SiCSi, 120.6(9); ClCCl, 110.9(16); SiCCl, 106.3(3)°.