Electron Energy Distribution Functions in CO2 Laser Mixture: The Effects of Second Kind Collisions from Metastable Electronic States

Electron energy distribution functions (eedf) in CO₂ laser discharge (He—CO₂—N₂—CO mixture) have been calculated by solving the Boltzmann equation in the presence of given concentrations of excited (vibrational and electronic) states. The results show a well structured eedf as a result of second kind collisions coming from metastable electronic states of N₂ and He as well as a strong dependence of rate coefficients for CO₂ dissociation and for the ionization of the different species.     

Electron energy distribution function in helium discharges: The role of superelastic collisions from He(3S)

Electron energy distribution functions (EDFs) in helium discharges have been calculated by solving the Boltzmann equation in the presence of given concentrations of the metastable He(³S) state. The results show that the presence of very small concentrations of such a state strongly modifies EDFs through superelastic (second kind) collisions, the effect being the larger the lower the reduced electric field E/N is.     

Excitation and quenching of ultraviolet nitrogen bands in the mixture of N2 and O2 molecules

Total quenching rate coefficients of three singlet and three triplet states of molecular nitrogen in the collisions with O₂ molecules are calculated on the basis of quantum-chemical approximations. The calculated rate coefficients of electronic quenching of N₂^? molecules are compared with the available experimental data. An influence of collisional processes on vibrational populations of electronically excited N₂(a¹Π_g) and N₂(A³Σ_u⁺) molecules is studied for conditions of laboratory discharge in N₂ and O₂ at admixtures of molecular oxygen 0%-20% for the pressures 1-1000 Pa. It is indicated that molecular collisions cause changes in relative populations of vibrational levels of these states and intensity relations of ultraviolet bands of N₂ with rise in the pressure and the O₂ admixture.     

On the coupling of electron energy distribution function and excited state distributions in pulsed microwave H$\mathsf{_{2}}$ plasmas

Time evolution of vibrationally and electronically excited states and their coupling with the electron energy distribution function (EEDF) were calculated for microwave pulsed discharges. Different situations have been considered by changing the period and the duty cycle, and considering different pressure values.The main result of this study was to evidence the change in the non-equilibrium character and dynamics of the different distributions depending on the pressure and the pulse period. In particular EEDF strongly deviating from the Maxwell behaviour appear as a consequence of inelastic and superelastic collisions at relatively high pressure and long period. Also, strong oscillation appears on the tail of the H₂ vibrational distribution at high pressure discharge conditions. At low pressure, the effect of superelastic and inelastic collisions appears to be less significant and most of the plasma characteristics may be deduced from a time averaged electron energy distribution function.Received: 15 January 2004, Published online: 29 June 2004PACS: 52.25.Dg Plasma kinetic equations - 52.20.Hv Atomic, molecular, ion, and heavy-particle collisions - 52.27.Cm Multicomponent and negative-ion plasmas     

Selfconsistent Electron Energy Distribution Functions in Non Equilibrium oxygen: Effects on the Dissociation Rate

Electron energy distribution functions (edf) in non equilibrium oxygen have been calculated by solving the Boltzmann equation coupled to a system of vibrational master equations. The results show the importance of both superelastic vibrational collisions and of the presence of oxygen atoms in affecting edf. The coupling between the Boltzmann equation and the system of vibrational master equations brings to a temporal evolution of edf, which progressively changes from a cold molecular gas situation (all molecules in the ground vibrational level) to a vibrationally excited molecular gas and finally to a gas composed by oxygen molecules and oxygen atoms. All electronic rate coefficients follow a temporal evolution. due to the corresponding evolution of edf. Finally the present results are used for discussing the dissociation rate of molecular oxygen in electrical discharges.     

Determination of the rate coefficients for the collisional excitation and de-excitation of the upper laser levels of Ar

The absolute concentrations of the argon-ion states of the configurations 3d, 4s, 4p, 4p′, 4d and 5s have been measured for a pulsed laser discharge whose plasma parameters have been previously determined. For the resonant levels, the measurements were made by a self-absorption technique and for other levels by absolute spectroscopic observations. Variations of the populations of these levels as functions of discharge current and filling pressure (i.e. electron temperature and density) permitted calculations of the total excitation and de-excitation rate coefficients due to electrons as functions of temperature for each laser level. For excitation, collisions with the fundamental and long-lived states were taken into account while, for de-excitation, superelastic, excitation and ionization collisions were considered.     

Experimental investigation of ultracold atom-molecule collisions

Ultracold collisions between Cs atoms and Cs2 dimers in the electronic ground state are observed in an optically trapped gas of atoms and molecules. The Cs2 molecules are formed in the triplet ground state by cw photoassociation through the outer well of the 0-(g) (P3/2) excited electronic state. Inelastic atom-molecule collisions converting internal excitation into kinetic energy lead to a loss of Cs2 molecules from the dipole trap. Rate coefficients are determined for collisions involving Cs atoms in either the F=3 or F=4 hyperfine ground state, and Cs2 molecules in either highly vibrationally excited states (nu'=32-47) or in low vibrational states (nu'=4-6) of the a3 summation(u)+ triplet ground state. The rate coefficients beta approximately 10(-10) cm3/s are found to be largely independent of the vibrational and rotational excitation indicating unitary limited cross sections.     

Electronic excitations on clean and adsorbate-covered oxide surfaces

We have studied electronic excitations at the surfaces of NiO (100), Cr₂O₃(111), and Al₂O₃(111) thin films with Electron Energy Loss Spectroscopy (EELS). On NiO (100) we observe surface electronic excitations in the energy range of the band gap which shift upon adsorption of NO. Ab initio cluster calculations show that these excitations occur within the Ni ions at the oxide surface. The (111) surface of Cr₂O₃ is characterized by distinct excitations which are also strongly influenced by the interaction with adsorbates. Temperature-dependent measurements show that two different states of the surface exist which are separated by an activation energy of about 10 meV. For Al₂O₃(111) we present data for a CO adsorbate. The oxide is quite inert with respect to CO adsorption as indicated by desorption temperatures between 38 K and 67 K. Due to the weak interaction with the substrate the a³II valence excitation of CO shows a clearly detectable vibrational splitting which has not been observed previously for a CO adsorbate in the (sub)monolayer coverage range. For several different adsorption state the lifetimes of the a³II state could be estimated from the halfwidths of the loss peaks, yielding values between 10^–15 s for the most strongly bound species and 10^–14 s for the CO multilayer.     

Vibrational relaxation of KrF* and XeCl* by rare gases

A steady-state, chemiluminescence technique has been used to measure effective rate constants for vibrational relaxation as a function of vibrational level for KrF^* in collisions with He, Ne, and Ar and XeCl^* with Ar. The effective rate constants reported include contributions to relaxation due to intersystem crossing between theB andC states, in addition to direct relaxation within theB state. The relevance of these results to the understanding of previous measurements in KrF and XeCl lasers is discussed.     

Calculation of radiative transition probabilities and radiative recombination rate coefficients for H2, OH, H 2+ and OH+ molecules

A method is presented to calculate the radiative transition probabilities and the radiative recombination rate coefficients between electronic molecular states. Total transition probabilities are determined from vibrational transition probabilities without considering the detailed rotational structure of the molecular electronic states. Radiative recombination rate coefficients are obtained from the computation of vibrational photo-ionisation cross sections. Concerning spontaneous emission, Lyman (B → X) and Werner (C → X) band systems of H₂ and Meinel (A → X), (B → A) and (B → X) band systems of OH are investigated. For radiative recombination, transitions between H₂⁺ (X) and H₂(X), and between OH⁺(X, a, A, b, and c) and OH(X) are considered. Transition probabilities and recombination rate coefficients are calculated as a function of temperature in the range 1500–15 000 K.     

Low temperature vibrational relaxation of OD in the A2Σ, state

The vibrational relaxation of the A ²Σ state of OD has been studied in the low translational temperature environment of an argon free-jet (T_trans near 5 K). Using laser induced fluorescence (LIF), the absolute vibrational relaxation rate coefficients were measured for OD A²Σ (ν′) to be 7.1 ± 2.6 × 10^?11, 5.9 ± 1.4 × 10^?11, and 2.7 ± 1.1 × 10^?11 cm³ s^?1 for the ν = 3, 2 and 1 states, respectively. State-to-state relaxation rate coefficients were also obtained for the ν= 1, ? = 1 level going to ν= 0, ? levels in the A²Σ manifold. The rotational relaxation rate coefficient for ν= 1, ?= 1 in the A state of OD was found to be 9.6 ± 1.0 × 10^?11cm³s^?1. These values are consistent with values measured for OH A²Σ, and the total loss rates are near the capture rate coefficient value. The vibrational relaxation rate coefficients k_ν appear to be governed by the vibrational energy of the molecule rather then by interaction with nearby dissociative states such as the a⁴Σ state. The relative Einstein A factors for the A²σ (ν = 3) state of OD were determined and compared with the available calculated value.     

Vibrational fluorescence from NaBr:CN- centres induced by electronic excitation

Infrared fluorescence from higher vibrational states has been obtained for NaBr:CN^- centres by optically exciting the electronic uv-absorption with an excimer laser at 193 nm. The decay time of the ir-signals is 580 μs for all five observed emission lines being limited by a slow relaxation of the electronic excited state (a³π). The delayed buildup of the ir-signals (180 μs for 2 → 1, 30 μs for 4 → 3) indicates a successive population of the vibrational levels.     

Electron Energy Distribution Functions in RF Molecular Plasmas: The Role of Second Kind Collisions

Electron energy distribution functions in rf molecular plasmas have been calculated by solving the time dependent Boltzmann equation in the presence as well as the absence of vibrationally and electronically excited molecules and thus of first kind and second kind (superelastic) collisions with them. The results, which refer to a model plasma composed by three components (the ground state, a lumped vibrational state and a lumped electronic state), show that these collisions with vibrationally and electronically excited molecules strongly affect the modulation of the electron energy distribution function and related quantities.     

Emission Spectra of BeO in Near Ultraviolet Region

Abstract

The emission spectra of isotopic BeO molecules as excited in low-pressure arc have been photographed in the region 300–350 nm at medium dispersion. The bands have been assigned to the c³II ? a³II system. The vibrational numbering was obtained from a study of the vibrational isotope effect. Vibrational constants for involved states are derived from least-squares fits of the measured bandhead wavenumbers.     

Helium and self-broadening in the first and second overtone bands of 12C16O

The pressure broadening coefficients for rotation-vibration lines of J states up to 22 in the 2-0 band and J states up to 20 in the 3-0 band of pure CO and HeCO mixtures were measured. The data were obtained at room temperature utilizing a Fourier transform spectrometer and various cells, including a 113-m White cell. These data exhibit little change with increasing vibrational level, and in the case of helium broadening, only slight J dependence.     

Resonances and chaos in the collinear collision system (He,H 2 + ) and its isotopic variants

The collinear atom-diatom collision system provides one of the simplest instances of chaotic or irregular scattering. Classically, irregular scattering is manifest in the sensitive dependence of post-collision variables on initial conditions, and quantally, in the appearance of a dense spectrum of dynamical resonances. We examine the influence of kinematic factors on such dynamical resonances in collinear (He, H ₂ ⁺ ) collisions by computing the transition state spectra for collinear (He, HD⁺) and (He, DH⁺) collisions using the time-dependent quantum mechanical approach. The nearest neighbor spacing distributionP(s) and the spectral rigidity Δ₃(L) for these resonances suggest that the dynamics is predominantlyirregular for collinear (He, HD⁺) and predominantlyregular for collinear (He, DH⁺). These findings are reinforced by a significantly larger “correlation hole” in ensemble averaged survival probability ≪P(t)≫ values for collinear (He, HD⁺) than for collinear (He,DH⁺). In addition we have also examined measures of classical chaos through the dependence of the final vibrational action,n _f, on the initial vibrational phaseφ _i of the diatom, and Poincaré surfaces-of-section. They show that (He, HD⁺) collisions are partly chaotic over the entire energy range (0–2.78 eV) while (He, DH⁺) collisions, in contrast, are highly regular at collision energies below the classical threshold for reaction. Above the threshold, the scattering remains regular for initial vibrational statesv=0 and 1 of DH⁺.     

Submillimeter-Wave Spectroscopy of CO in the aΠ State

Submillimeter-wave absorption spectrum of CO in electronically excited a³Π state was observed in the 540–830 GHz region by using a phase-locked BWO spectrometer. New rotational transitions up to J = 9–8 in the vibrational excited states up to v = 5 were analyzed accompanied with previous observations in the RF and millimeter-wave regions. A multivibrational states fit among a′ ³Σ⁺ (v = 0–3) and a³Π (v = 0–7) states was performed in order to analyze overall perturbation between the a³Π and a′ ³Σ⁺ states. As a result, the deperturbed rotational parameters were derived precisely to improve the RKR potential.     

Angular dependence of double electron capture in collisions of C4+ with He

In charge-transfer collisions of C⁴⁺(1s^{2 1}S) with He (1s^{2 1}S), the process of double electron capture into the ground state C²⁺ is well-known to dominate other channels by an order of magnitude for projectile energies below 10 keV. This work presents a calculation of differential cross-sections resolved in the angle and energy gain variables, based on an ab initio treatment of electronic states, and compares with the measurements published in the literature (projectile energy E=270, 400, and 470 eV). We also briefly discuss the semi-empirical two-state models developed by experimentalists for this process.     

Inelastic collision cross section of excited molecules

The (v′=6,J′=43) level in theB ¹Π _u electronic state of Na₂ has been selectively populated by excitation with the 4 880 Å line of the argon laser. Through collisions with He atoms energy is transferred to neighbouring rotational states in Na₂ and the density of these states is determined by observing fluorescence to electronic ground state. From previous measurement of the lifetime of theB ¹Π _u state and new measurements of the intensities of collision induced spectral lines as a function of He pressure, absolute collision cross sections for all rotational transitions up to ΔJ=±5 have been obtained. The total cross section for all rotational transitions observed is σ _rot ^total =65±15 Ų. Preliminary results about collision induced vibrational transitions are also presented.