Rapid interspecies energy flow between vibrationally excited SF6 and the asymmetric stretch of N2O

Rapid, selective collision-dependent excitation of N₂O following pumping of SF₆ with a CO₂ laser is reported. The N₂O fluorescence rise depends on the pressure of each component and is dominated by the SF₆-dependent contribution of 2290 ms^?1 Torr^?1. The subsequent fall is governed by V→V processes among SF₆ vibrational modes.     

Vibrations and dissociation of molecules in strong electric fields: N2, NACl, H2O and SF6

The static deformations and vibrations of the title compounds with an applied static electric field have been studied by density functional theory calculations. It is found that for diatomic molecules, bond length and vibrational frequency as a function of the field can be fit very well all the way up to the dissociation limit by an analytical formula derived from a Morse potential model including an additional external field term. Polyatomic molecules show more complex behaviour with a single mode becoming soft at the dissociation limit. The frequency of the soft mode near the critical field is again described well by the analytical model. The vibrational analysis shows that in polyatomic molecules dissociation proceeds as a heterolytic fragmentation process, which can break the symmetry of the molecule in the applied field.     

Fixman—rider extended diffusion model for linear molecules. Application to N2O dissolved in liquid SF6

The diffusion model proposed by Fixman and Rider and applied to spherical tops is extended here to linear molecules. The infrared and Raman rotational correlation functions are compared to experimental functions that are obtained for N₂O in liquid SF₆ at different temperatures. It is possible to find a good fit either in infrared or in Raman, but not in both techniques simultaneously.     

Energy transfer among excited vibrational states of SF6

Studies of the risetime of laser induced 16μ fluorescence in SF₆ show the rapid equilibration (1.5 μsec torr) among the excited vibrational states. The subsequent decay of fluorescence consists of 2 exponentials. The faster of these is due to vibration-translation energy transfer (160μsec torr) and the slower is due to thermal cooling of translationally hot gas.     

Deactivation of vibrationally excited N2 by H2O

The VV exchange rate for the N₂H₂O system is determined using a hard-core repulsive potential. It is found that the rapid deactivation rate arises from near-resonant VR exchanges involving non-dipole changes in the rotational states. Furthermore, a classical-path approximation is used and the resulting rate found to be critically dependent on the path chosen.     

Vibrational excitation of SF6 scattering from graphite

We have observed vibrationally excited sulfur hexafluoride molecules in direct inelastic scattering from hot graphite surfaces. The vibrational temperature for the scattered flux has been determined by probing the effect of internal temperature on electron-induced fragmentation observed in mass spectra. The vibrational excitation depends on incident translational energy, E_tr, and a maximum temperature increase of 50 K is reached in direct scattering at E_tr = 2.5 eV. No effect of surface temperature has been observed at 950–1400 K. Inelastic angular distributions are reproduced by a collision complex model, and the experimental results are related to existing models for vibrational excitation.     

Resonance energy transfer from Al2O3 to adsorbed N2O

Radiolysis of adsorbed N₂O is shown to occur due to both the dissociative capture of electrons and direct energy transfer from the excited states of alumina to N₂O. One excited state ensures the decomposition of three N₂O molecules.

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, N₂O , N₂O, N₂O.

     

Time-resolved investigation of the de-excitation of xenon excimer by SF6 and N2 excited with synchrotron radiation

An attempt has been made 'o measure the rate constant for the de-excitation of a state-specified excimer using the pulse character of synchrotron radiation. The rate constants have been obtained for de-excitation of a vibrationally relaxed excimer Xe₂^*(O_u⁺; low v) by SF₆ and N₂ as 9 × 10^?10 and 7 × 10^?12 cm³ molecule^?1 s^?1 respectively.     

Vibrational energy transfer from N2 to CO on electron excitation of N2-CO solids at 4.2 K

Spectra emitted from 0.1% CO-N₂ solids excited with high energy electrons at 4 K show evidence for resonant transfer of vibrational energy from highly excited vibrational levels of N₂ to CO in the process N₂(X¹Σ_g⁺, ν) + CO(ν = 0) → N₂(X¹Σ_g⁺, ν - 1) + CO(ν = 1) + phonons. Energy transfer from levels with ν ? 9 has been observed.     

Possible cyclic triatomic molecules including N2O and O3

Proposed metastable cyclic conformations of N₂O⁺ and O₃, have been examined by INDO and ab initio calculations. INDO is found to exaggerate the stability of possible cyclic species. In ab initio calculations a multi-dimensional energy surface must be explored. With a [5, 3] basis SCF calculations yield a trivariate local minimum for cyclic O₃. However, for N₂O, N₂O⁺ and O²⁺₃, starting from cyclic “bonded” structures, paths involving asymmetric deformations run downhill in energy to a diatomic molecule and a separated atom. A paradox concerning the removal of an electron from an antibonding orbital in a cyclic molecule is resolved.     

Vibrational relaxation of CO2(00°1) and N2O(00°1) by NO

The far-from-resonance transfers and the de-excitation processes in CO₂-NO and N₂O-NO systems have been studied by measuring fluorescence decay rate constants of CO₂ or N₂O excited to the (00°1) level by laser radiation. The diagrams giving the variations of these rate constants versus the molar fraction of CO₂ or N₂O have been set out. From these diagrams, the relative importance of the V-V transfer and V-T de-excitation rate constants is discussed. The transfer rate constants have been calculated from a semiclassical theory in which the interaction potential is a sum of four atom-atom Morse potentials. The disagreement observed between calculated and experimental values probably results from the attractive multipolar forces which the theory does not take into account.     

Temperature dependence of the vibration-vibration transfer rates from CO2 and N2O excited in the (0001) vibrational level to 14N2 and 15N2 molecules

V-V transfer rates from CO₂ and N₂O excited in the (00⁰1) vibrational level to ¹⁴N₂ and ¹⁵N₂ are determined from 150 to 1200 K using the laser fluorescence method, and compared with values calculated on the basis of dipole-quadrupole interactions.     

PVTx measurements for N2O + CH3F, N2O + CH2F2, and N2O + CHF3 binary systems

Isochoric PVTx measurements have been performed for the binary system of nitrous oxide + CH₃F (R41), +CH₂F₂ (R32), and +CHF₃ (R23) using a new experimental set-up. The experiments covered both the two-phase region and the superheated vapor region and were performed within the temperature range 214–358 K and within a pressure range from 270 to 5600 kPa. Data have been collected for not less than four compositions for each system. The vapor–liquid equilibrium data were derived correlating the experimental data by means of the Carnahan–Starling–De Santis equation of state. The studied systems show a positive deviation from the Raoult's law. The results obtained were compared with the Burnett PVTx data. The two methods showed a mutual consistency within an acceptable margin of error. No other experimental PVTx data were found in the literature for these binary systems.     

Raman analysis of SF6 molecular beams excited by a cw CO2 laser

In a molecular beam the effects of vibrational pumping of SF₆ (ν₃ = 948 cm^?1) are studied, using a line-tunable cw CO₂ laser. Intracavity spontaneous Raman scattering is used for analysis. For excitation in the collision regime (x_E/D ≤ 1), a thermal redistribution of the ν₃ excitation over all vibrational modes is found, together with an average absorption up to six photons per molecule. The infrared absorption profile shows a red-shift of 6 cm^?1. For excitation in the relatively rare collision regime (x_E/D ? 4), a structured non-thermal ν₁ Raman spectrum is observed, especially in the case of seeded molecular beams (10% in He). The observed hot-band peaks can be explained in terms of single-photon absorptions and collision-induced near-resonant V-V energy transfer, leading to single, double and triple excitations of the ν₃ mode. The value of T_rot in the beam is found to influence sensitively the non-resonant energy-transfer rate [e.g. hν₃(948 cm^?1)+ΔE_rot → h(ν₄ + ν₆)(962 cm^?1) relative to the near-resonant transfer rate (hν₃ + hν₃ → 2hν₃ + 3.5 cm^?1)].     

Vibrational relaxation in SO2

SSH—Tanczos calculations are carried out to estimate the energy transfer probabilities and the slow vibrational relaxation time in SO₂ in the temperature range 300–2000 K. The theoretical results suggest a series process below 1000 K, and a complex series/parallel process above that temperature for the vibrational relaxation in SO₂. The theoretical results are compared with the known experimental data.     

Vibrational excitation of SF6 in collisions with He atoms

Vibrational excitation of SF₆ molecules in collisions with He atoms is studied using a vibrational close-coupling, rotational infinite-order-sudden method of calculation. Integral and differential cross sections for excitation of the triply degenerate ν₆ and ν₅ vibrational modes of SF₆ are reported for thermal collisional energies. Excitation of the ν₆ mode is found to be particularly efficieny. The cross sections are much larger than those calculated previously for the excitation of the bending mode in the He + CO₂ system. The differential cross sections are backward peaked.     

Vibrational energy distribution of CsF produced by reactive beam scattering of Cs by SF6 and SF4

The molecular beam electric resonance method has been used to measure the vibrational energy distribution of CsF produced in the chemical reactions Cs + SF₆ and SF₄. The reaction Cs + SF₆ yields a perfect Boltzmann distribution for the products CsF. For the reaction Cs + SF₄ a more complicated distribution has been found which, according to the molecular structure of SF₄, can be explained as a superposition of two Boltzmann distributions of different vibrational temperatures.     

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.     

Lifetime measurements of the excited states of N2 AND N2 by laser-induced fluorescence

Absorption and fluorescent scattering of nitrogen laser radiation by a low-pressure RF laboratory plasma (n_e = 10¹² cm⁻³) has been observed for the first negative system of N₂⁺. A 67±1 ns lifetime of N₂⁺ (B ²Σ_u⁺) was experimentally measured from the laser-induced fluorescence. In addition, enough collisionally excited N₂ (B ³Π_g) was produced to observe laser-induced fluorescence for the second positive system of N₂. The lifetime of N₂ (C ³Π_u) was found to be 41±2 ns. The measured lifetimes are in good agreement with published values calculated from theory.     

Vibrational relaxation of CO2 laser excited SiF4 gas in binary mixtures

Vibrational relaxation rates for SiF4 in binary mixtures with CO₂, CH₄, O₂, N₂, He and Ar are determined using CO₂ laser-induced visible fluorescence. A model for the process is discussed.