Dynamical treatment of binding,polarization and recoil in asymmetric ion-atom collisions

The cross sections for quenching the lowestn ² P states of the alkali atoms Li, Na, K., and Rb by the inert gases He, Ne, Ar, Kr, and Xe are presented for 5 eV≦E _c.m.≦ 100 eV. These cross sections are derived from the corresponding cross sections for collisional excitation by applying the principle of microreversibility. Upper estimates for the quenching cross sections at thermal energies are given; in all studied cases the quenching cross sections are <8·10^?3Ų. These new upper limits are in most cases much lower than those obtained from other methods previously.     

The ZnHg excimer: Optical and kinetic properties

The optical and collisional properties of the ZnHg excimer have been examined by optically pumping the Zn (4¹S₀→ 4³P₁) resonance line in Zn-Hg vapor mixtures. The stimulated emission cross-section determined for ZnHg¹ (2.3 × 10^?19 cm²) and the excimer's low rate of quenching by Hg (5.5 × 10^?15 cm³ s^?1) make it attractive for future energy-storage laser research.     

Infrared transitions of C2D6 from v 4 to the interacting system v 4+ v 6, v 4+ v8, v 3+ 2v 4: rotational analysis,and torsional splitting in the v 3+ 2v 4 and v 3+ v 4 states

The hot infrared transitions of C₂D₆ from the υ₄(A_1u ) to the υ₄ + υ₆(A_2g ) and υ₄ + υ₈(E _g ) vibrational states, observed from 960 to 1180 cm^?1, have been rotationally analysed on a high-resolution Fourier transform spectrum (full width at half-maximum about 0·0030 cm^?1). The vibration-rotation interactions affecting the upper vibrational states are very similar to those of the corresponding cold system. A strong x,y Coriolis interaction between υ₄ + υ₆ and υ₄ + υ₈, with K-level crossing, generates large displacements of the rotational components of both vibrational states, tuning them to additional local resonances in several spectral regions. Thus l resonances with Δl = ±2, Δk = ±1 occur within υ₄ + υ₈. A x,y Coriolis-type resonance between υ₄ + υ₈(?l,K ? 1) and υ₃ + 2υ₄(K) occurs at K = 11,12,13, and a further coupling of υ₄ + υ₈(+l,K + 1) and υ₃ + 2υ₄(K + 3) is most effective at K = 11 and 12. These resonances induce torsional splittings on the perturbed levels of υ₄ + υ₈ and allow us to determine the torsional splittings in the υ₃ + 2υ₄ state. The vibration-rotation constants of υ₄ + υ₆, υ₄ + υ₈ and υ₃ + 2υ₄, several interaction parameters and the torsional splitting of υ₃ + 2υ₄ have been determined by least-squares fit of 1391 observed transition wavenumbers, with an overall standard deviation σ = 0·75 × 10^?3 cm^?1. The vibrational wavenumbers found for the four torsional components of (υ₃ + 2υ₄)? υ₄ are υ(E_3d) = 1040·961 82(809)cm^?1, υ(A_3d) = 1041·218 27(865)cm^?1, υ(E_3s) = 1041·225 23(662)cm^?1 and υ(A_1s) = 1041·407 77(633)cm^?1. These are anomalous for both the order of the torsional components and the magnitudes of their separations. We believe that this is mainly due to the interactions of υ₃ + 2υ₄ with the torsional manifolds with υ₃ = 0 and υ₃ = 2, through the vibration-torsion Hamiltonian term (?V ₆/?q ₃)q ₃cos (6γ)]/2. The further observation of a few doublets of υ₈ and υ₃ + υ₄ at resonance provides information on the torsional splitting of the latter state.     

Infrared diode-laser spectrum of the CH3CN ν2 band: Analysis of local resonances with ν6±1 + 2ν8±2, ν4 + ν7±1 + ν8±1, ν4 + ν6±1, ν4 + ν7±1, and 2ν70 + ν8±1 states

Fifty-one sections of infrared diode-laser spectra of acetonitrile have been measured in the region from 2283.5 to 2235.7 cm^?1. About 450 transitions belonging to the ν₂ band have been assigned for K ≦ 7 and J ≦ 44. Anomalies found in the rotational structure have been proven to be due to five local resonances. Observed transition frequencies have been fitted by a least-squares method to a model which includes Fermi-type resonances (Δk = 0, Δ? = ± 3n) with ν₆^±1 + 2ν₈^±2 and ν₄ + ν₇^±1 + ν₈^±1 states, x, y-type Coriolis resonances (Δk = ±1, Δ? = ?3n ± 1) with ν₄ + ν₆^±1 and ν₄ + ν₇^±1 + ν₈^±1 states, and a centrifugal-distortion-type resonance (Δk = ±2, Δ? = ?3n ± 2) with a 2ν₇⁰ + ν₈^±1 state. The 11 × 11 dimensional energy matrix has been diagonalized in order to obtain the perturbed energy levels. The standard deviation for the fit is 1.075 × 10^?3 cm^?1. The molecular constants determined are also listed.     

Negative Ions,Ozone, and Metastable Components in dc Oxygen Glow Discharge

In a dc glow discharge in oxygen, the concentrations of minor components of O₂(a¹Δ_g), O₂(b¹ Σ_g), O₃, O(¹D), as well as nagative ions and electrons have been measured. Balance equations have been derived which describe satisfactorily the stationary concentrations of these components as functions of gas pressure and discharge current. For the first time, the rate constants of important aeronomical reactions (a) O^? + O₂(a¹Δ_g) → O₃ + e, (b) O₂^? + O₂(a¹Δ_g) → 2O₂ + e and (c) e + O₃ → O₂^? +O have been measured as functions of gas temperature T and mean energies of ions E_i and electron E₆: K_a = (2.5 ± 0.5) · 10^?9 · (T/300)^{4 ± 0.4}· (E_i/0.04)^{?2.6 ± 0.4} cm³/s for T = 385?605 K and E_i = 0.10 ? 0.66 eV; K_b = (1.0 ± 0.3) · 10^?10 · (T/300)^{?2 ± 0.5} · (E_i/0.04)^{0.23 ± 0.05} cm³/s for T = 330?605 K and E_i = 0.09 + 1.5 eV; K_c for E_e = 0.8÷5 eV.     

Zeeman spectroscopy of the 4 Eu → 2 B 1g phosphorescence of copper porphin in an n-alkane single crystal

The phosphorescence spectrum of the metastable ⁴ E_u state of copper porphin in single crystals of n-octane (C₈) and n-decane (C₁₀) has been studied between 2·3 and 35 K, with and without a magnetic field B. The crystal field splitting between the orbital components observed at 35 K is δ = 30·3 ± 0·3 (C₈), 13·8 ± 0·2 cm^-1 (C₁₀). From the Zeeman shifts we derive the effective orbital angular momentum Λ′ = 0·8 ± 0·2 (C₁₀), the spin-orbit coupling parameter |Z′| = 1·5 ± 1·0 cm^-1 (C₁₀), the spin-spin dipolar interaction parameters D = -0·1 ± 0·2 cm^-1 (C₈, C₁₀) and |E| = 0·31 ± 0·03 cm^-1 (C₈, C₁₀), and the g-factors g _∥ = 2·14 ± 0·04 (C₈, C₁₀) and g _⊥ = 2·00 ± 0·03 (C₈, C₁₀).     

Messung der Wirkungsquerschnitte für die Linienverbreiterung von Hochfrequenzübergängen im 63 P 2-Zustand des Quecksilbers durch Stöße mit Edelgasatomen

The linewidth of high frequency transitions between Zeeman-levels of the metastable 6³ P ₂-state of mercury is measured as function of the pressure of various noble gases. The measurements are made for all noble gases in the pressure range from 10^?3 to about 2 · 10^?2 Torr. The cross sections for linebroadening due to atomic collisions are derived from the pressure dependence of the linewidth. These cross sections σ were found to be (71 ± 10) · 10^?16 cm² for He, (82 ± 10) · 10^?16 cm² for Ne, (153± 12) × 10^?16 cm² for Ar, (204±28) · 10¹⁶ cm² for Kr and (291 ± 41) · 10^?16 cm² for Xe.     

N2(B3IIg) Quenching by Ethanol

The reaction rate values for the molecular nitrogen B³II_g state quenching by ethanol for vibrational quantum numbers v′ = 4–12 have been evaluated from the change of N₂ first positive system spectrum at ethanol addition to a high speed, microwave produced, plasma flow. The wall influence is avoided using a 0.9 m large reaction chamber. Computed N₂(B³II_g) quenching rate values are comprised between 0.9 × 10^?10 and 1.4 × 10^?10 cm³ · s^?1, being smaller than the corresponding gaskinetics rate.     

Twenty-parameter eigenfunctions and energy values of the 23 S States of He and He-like Ions

Twenty-parameter calculations of the energies and wave functions of the first excited states 2³ S of He, Li⁺, Be⁺⁺, B⁺⁺⁺, O⁶⁺, Ne⁸⁺, Mg¹⁰⁺, have been carried out using Hylleraas' method. The energy values have been corrected for mass polarization. The coefficients of the best wave functions are listed. Similar calculations for the 2³ S state of the H^? ion yield an energy value which cannot be distinguished from the energy of a free H atom. For He and Li⁺, in addition, forty-parameter calculations have been carried out. The results compare well with the recent calculations of Pekeris using a somewhat different method. Even after the inclusion of the relativistic correction, the theoretical energy values deviate slightly from the observed. The differences, ?0·10±0·05 cm^?1 for He and ?1·07±0·10 cm^?1 for Li⁺, represent observed values of the Lamb shifts in the 2³ S states. These values agree within their uncertainties with the values predicted from quantum electrodynamics.     

A high resolution FTIR spectroscopic study of the hydrogen-bonded heterodimer H3N−HCN

The spectrum of the symmetric top, hydrogen-bonded heterodimer H₃N?HCN has been recorded between 2900 and 3200cm^?1 using a high resolution FTIR spectrometer. The more intense bands are associated with the ν₂ (H?CN stretch) vibration and include hot bands associated with the low frequency modes ν₅, ν₂ and ν₁₀. Weaker difference bands of the type ν₂+(n?1) ν5?nν₅ are also observed. Analysis of the bands yields values for the band origins: ν2/0=3110·5±0·2cm^?1 and ν5/0=140±5cm^?1 and the anharmonicity constants: x _2,10=12·7±0·5cm^?1, x _2,9≈x _2,5=23±3cm^?1 and x _5,10=?5±2cm^?1. The lifetime in ν₂ with respect to vibrational predissociation, estimated from the width of the sharpest observed feature, is 100?200 ps but there is some indication that this lifetime may decrease at high J.     

Anregung metastabiler Zustände von Barium und Thallium durch Atomstöße im Stoßwellenrohr

It is shown that relaxation times for the excitation of metastable levels of Ba and Tl by collisons of the ground state atoms with carrier gases Ne and Ar can be measured with good accuracy behind reflected shock waves (2700≦T≦3300 °K) by means of two-channel atomic line absorption spectroscopy. Quenching cross-sections, which thus can be derived, cover in principle the range 10^?14 cm²<Q<10^?21 cm². In collisions with Ar one finds for the deactivation of Ba(¹ D ₂)Q=1.2 · 10^?19cm², of Ba(³ D ₁)Q=0.95 · 10^?19 cm² and of Tl(² P _3/2)Q<5 · 10^?21 cm² without noticeable temperature dependence. From this follows a) (on the basis of the Landau-Zener formula) that the pseudo-crossing of the potential energy curves of Ba-Ar takes place within 0.25 eV of the Ba(D) levels and b) that spin-orbit coupling is not rate controlling in the Ba(³ D ₁ →¹ S ₀) transition. The ratio of cross-sections for quenching of Ba(¹ D ₂) by Ar and Ne is about 3, suggesting that the polarizabilities of the noble gas collision partners play a major rôle in the transition probabilities. The mean self-quenching cross-sectionQ=5 · 10^?16 cm² of Tl(² P _3/2) at 3000 °K is about the same as the one reported for 1000 °K and it exceeds the self-quenching cross-section of metastable Ba by at least one order of magnitude.     

Resonance absorption and fluorescence in argon

Absorption cross sections of argon for argon resonance radiation have been measured by several techniques. The apparent cross sections are small (0·1 to 1·6 × 10^-18 cm²) for resonance absorption and the values depend on the technique used for measurement. These observations are interpreted in terms of extensive reversal and broadening in the source. The excitation and quenching of resonance fluorescence was studied to provide information about the rates of the processes

The rate constants were estimated relative to k _r, the rate constant for radiation. Radiation imprisonment leads to a reduction of k _r from its natural value and observations of the decay of resonance fluorescence suggest that k _r ～ 1·5 × 10⁵ s^-1 in our system at [Ar] = 2 × 10¹⁷ atom cm^-3. Combining this value with the relative values for the quenching rate constants gives k ₁ < 1·5 × 10^-13, k ₁′(M = N₂) ～ 6 × 10^-12, k ₁′(M = NO) ～ 4 × 10^-10, in units of cm³ s^-1 molecule^-1.     

Measurement of the hyperfine interaction of free75As ions In H2, He,Ne, Kr and Xe buffer environments and estimate of clolision cross sections in the eV and meV energy region

With the time-integral perturbed angular correlation (TIPAC) method the pressure dependence of the perturbation of the 121.1–279.5 keV γ-γ cascade in⁷⁵As has been investigated using gaseous H₂ ⁷⁵Se sources in different buffer environments. The obtained attenuation coefficients G₂₂ (∞) in the range of 0.55 to 1.0 were fitted with a theoretical stochastic model. In the region of low density, where the correlation time τ_C is large compared to the lifetime τ of the intermediate level of the nucleus, charge transfer collision cross sections have been evaluated between 8.1·10^?16 cm² for He, 1.3·10^?14 cm² for Xe and 1.8·10^?14 cm² for the molecular H₂ buffer gas. For increasing densities of the buffer gases the correlation time τ_C became small compared to the intermediate lifetime τ. The main effect in this region is the depolarization, and we found cross sections between 5.2·10^?15 cm² for He, 8.7·10^?14 cm² for Xe and 1.2·10^?13 cm² for the H₂ buffer gas.     

Remeasurement of the low-energy cross section for the 15N(p, α0)12C reaction

The cross section for the ${}^{15}\text{N(p}\text{, α}{}_0\text{)}{}^{12}\text{C}$ reaction has been measured at θ_lab = 135° over the proton energy range 93 ≦ E_p ≦ 418 keV. The results are in good agreement with the less precise but much earlier measurements of Schardt, Fowler and Lauritsen (1952). An analysis of the present data in terms of a two-level calculation including the 338 keV (1^?) and 1028 keV (1^?) resonances determines a zero-energy intercept for the astrophysical S-factor of S(0) = 78 ± 6 MeV · b.     

Measurement of the lifetime and quenching rate of metastable 2S muonic helium ions

The lifetime of the 2S state in (μ^?4He)⁺ ions has been measured at He-gas pressures between 50 Torr and 6 atm (T=300 K). We observed both X-rays from the two-photon 2S→1S transitions as well as delayed K_α X-rays associated with radiative quenching. The quenching rate is strongly pressure dependent; it is predominantly a quadratic function of pressure with a measured three-body rate coefficient k=(5.9±0.8)×10^?32cm⁶/s. At 6 atm, we find τ_2S<250 ns because of the absence of two-photon transitions.     

Di-urethanesil hybrid electrolytes doped with Mg(CF3SO3)2

Two siloxane-based di-urethanesil frameworks incorporating poly(oxyethylene) (POE) chains have been synthesized by the sol–gel process and doped with magnesium triflate (Mg(CF₃SO₃)₂) with the goal of developing electrolytes for the fabrication of solid-state rechargeable magnesium batteries. In these matrices, short POE chains are covalently bonded to the siloxane network via urethane linkages. The xerogels have been represented by the notation d-Ut(Y) _n Mg(CF₃SO₃)₂, where Y?=?300 and 600 represents the average molecular weight of the POE chains and n stands for salt composition (molar ratio of OCH₂CH₂ units per Mg²⁺). Xerogels with compositions ranging from 2?≤?n?<?∞ were prepared. A crystalline POE/Mg(CF₃SO₃)₂ complex of unknown stoichiometry is formed in the d-Ut(300) _n Mg(CF₃SO₃)₂ materials with n?≤?6 and in the d-Ut(600) _n Mg(CF₃SO₃)₂ materials with n?≤?5. The organically modified silicate electrolytes with the highest conductivity of the d-Ut(300) _n Mg(CF₃SO₃)₂ and d-Ut(600) _n Mg(CF₃SO₃)₂ series are the samples with n?=?6 (3.9?×?10^?8 S cm^?1 at 26 °C and 8.7?×?10^?5 S cm^?1 at 97 °C) and n?=?100 (2.63?×?10^?7 S cm^?1 at 20 °C and 1.4?×?10^?5 S cm^?1 at 85 °C), respectively. Since the electrolytes for Mg batteries that have been proposed up to now have many intrinsic problems and although the room temperature conductivity values exhibited by the systems developed in the present study are still low in view of practical application, this work opens new directions for the development of solid-state Mg ion electrolytes.     

Photoelectron spectra of halides

High resolution photoelectron spectra, obtained with He I (584 Å) resonance radiation, are reported for ClF, ClF₃, BrF₃ and BrF (partial spectrum). In some cases Ne I (736–744 Å) radiation has also been used. Spinorbit and vibrational fine structure is resolved for the ground ²II states of ClF⁺ and BrF⁺; values obtained for ClF⁺ and ζ = 630 cm^-1, v′ = 870 cm^-1, and for BrF⁺ ζ = 2600 cm^-1, v′ = 750 cm^-1. From the vibrational envelope of the X ²∏ states, a bond length change of δr _e (-)0·10 Å for ClF⁺ and BrF⁺ is estimated. Ab initio SCF-MO calculations for ClF and ClF₃ are used to aid in the interpretation of the spectra via Koopmans' theorem. A considerable amount of charge delocalization in the trifluorides is inferred from the photoelectron spectra, and this is borne out by the calculations.     

Additivity and non-additivity of dissociation energies in intermolecular interactions. Theoretical studies on (H2)n,n = 2-8, (CO2)n,n = 2-6 and (HF)n,n = 2-8

CCSD(T) and MP2 results using the aug-cc-pV5Z basis set are reported for chain, cyclic and other structures of the clusters (H₂)_n, n?=?2-8, (CO₂)_n, n?=?2-6 and (HF)_n, n?=?2-8. In chain-like structures of (H₂)_n and (CO₂)_n, with the bonding type of the dimer maintained, the dissociation energy D_e of the dimer doubles for the trimer, triples for the tetramer, and so on. Due to these systems being dominated by short-range forces, interactions are essentially restricted to neighbouring monomers. For other types of (H₂)_n and (CO₂)_n structures, the multipliers relative to the dimerisation energy can be much higher. Dissociation energies for the hexamers in S₆ symmetry of both H₂ (379?cm^?1) and CO₂ (4925?cm^?1) are over ten times the respective dimerisation energies. For the chain-like trimer of HF, however, D_e is in excess of double the dimer value. Mainly due to longer-range dipolar forces, the interactions reach beyond the neighbouring monomers. The interaction energy between HF monomers in chains follows an approximate R^?2 (R being the F–F distance) relationship, The calculated dissociation energies of the HF octamer are 15,985?cm^?1 (factor of 10.4) for the chain, and 21,003?cm^?1 (factor of 13.7) for the C_6h cyclic structure.     

The density and pressure of helium in bubbles in metals

Abstract

The energy shift of the He 1¹S₀?2¹P₁ transition, ΔE(n), can be used to determine the density, n, of He in bubbles in metals. A self-consistent band structure calculation for solid fcc He yields a linear relationship ΔE=C.n with C _th=22 × 10^?3 eV nm³. Systematic electron energy loss spectroscopy and transmission electron microscopy studies of He bubbles in Al for various He doses and temperatures result in C_exp=(24±8).10^?3 eV nm³ in agreement with theory. The analysis is consistent with the assumption that dislocation loop punching is the dominant bubble growth mechanism during high-dose room temperature implantation. The application to He bubbles in Ni indicates a maximum He density of n=0.2 × 10³ nm^?3 for which He should be solid at room temperature.