Chemiluminescence studies of vibrational-to-vibrational energy transfer: MF3 + HF

The vibrational-to-vibrational energy transfer process, MF³ + HF (ν = 0) → MF + HF³ (ν ? 9) is studied by means of a “triple beam” experiment. Vibrationally excited MF³ molecules are created at the intersection of crude crossed beams of M (M = Na, Mg) and F₂. The metal fluorides thus formed then cross an HF beam, where energy transfer occurs. This is observed by measuring the overtone emission from HF. Upper bounds on the reaction cross sections for M ÷ F₂ are measured to be 135 ± 20 A² for M = Na and 80 ± 15 A² for M = Mg, and laser induced fluorescence is used to determine the vibration energy distribution of MgF, which peaks at 2.6 eV. The chemiluminescence signal from the overtone emission indicates a large vibrational interconversion cross section, which is estimated to be ? 30 A².     

Ionization of Na(3P) atoms by collisions with vibrationally excited nitrogen molecules in crossed molecular beams

A crossed molecular beam experiment is described in which the rate of ionization of Na(3P) atoms in collision with vibrationally excited N₂ molecul has been measured as a function of the N₂ temperature up to 3050 K. The activation energy in the experiment appears to be close to the ionization energy of the 3P level. An ionization cross section of about 100 »A² (excluding the activation energy factor) is derived with the help of a theoretical model. The limitations of the experiments as well as of the model are discussed.     

Rotational energy transfer in NO (A2Σ+, v = 0 and 1) studied by two-color double-resonance spectroscopy

Collision-induced rotational relaxation in the A²Σ⁺, v = 0 and 1 states of NO has been measured by using step-wise double-resonant ionization spectroscopy. Multiple quantum rotational energy transfer is occurring to at least |ΔJ| = 6 and the observed cross sections ranging from tens to hundreds of A² are larger than the gas-kinetic collisional cross section. The energy-transfer efficiency is slightly enhanced by the vibrational excitation. Energy-based scaling laws are successfully applied to reproduce the observed rotational distribution.     

Vibrational deactivation of CO2(0001) by ethane

The deactivation of CO₂(00⁰1) by ethane in the temperature range 300–600 K has been studied using a laser induced fluorescence technique. The energy transfer cross section decreased from 0.23 Ų at 300 K to 0.16 Ų at 600 K. The magnitude of the cross section is consistent with the expectation that near resonant V-V energy transfer processes are responsible for the energy transfer between CO₂(00⁰1) and ethane during collisions even though the observed temperature dependence of the energy transfer cross section does not follow that predicted by the existing theories.     

Surface-hopping model for near-resonant electronic energy transfer

A surface-hopping model is applied to near-resonant electronic energy transfer in the NFBi and O₂I systems. Multiple surface crossings occur in NFBi at ca. 8 A, corresponding well with measured transfer cross section of 200 A². A Landau-Zener model yields the temperature dependence of the thermally averaged cross section for the laser pumping reaction, O^*₂(a¹Δ) + I(²P_{$\text{3}\text{2}$}) → O₂(X³Σ^?_g) + 1^*(²P_{$\text{1}\text{2}$}).     

Massenspektrometrische untersuchungen des ionenstromes an der kathode anomaler glimmentladungen

A method for measuring the mass and energy distribution of the ion current at the cathode of anomalous glow discharges is described. A commercial hf time-of-flight mass spectrometer for residual gas analysis is combined with a newly developed energy analyzer. The method is used to analyse the mass distribution of ions of both high and low energy at the cathode of discharges in nitrogen and argon and to measure the energy distribution of the Ar⁺ ions in discharges in argon. By applying the theory of Davis and Vanderslice to this energy distribution the cross section for resonant charge transfer of Ar⁺ ions was determined. The results lie well within the range of values reported in the literature.     

Collisional ionization of alkali atoms by vibrationally excited N2

Chemiionization of alkali atoms by active nitrogen is studied in a crossed beam apparatus. Vibrationally excited N₂ in the electronic ground state is responsible for the ionization rather than electronically excited N₂ in the A ³∑_u⁺ state. The ionization cross section is of the order 10² A². The experimental data is consistent with the distribution of the vibrational levels of N₂ (X¹ ∑_g⁺) predicted by Bray or Caledonia and Center.     

Rotational relaxation in S1 glyoxal: Cross sections and a search for propensity rules

Details of rotational energy transfer from a few selected K′J′ levels in the zero point vibrational level of ¹Au(S₁) glyoxal vapor have been studied. The cross section for destruction of an initial K′J′ level by rotational relaxation in collision with ground electronic state glyoxal is about 240 A² or 4.5 times gas kinetic. Much of the rotational transfer within the S₁ state occurs with large ΔK′ and ΔJ′. No strong propensities for △K′ = 0, ± 1, ± 2, or ± 3 with small ΔJ′ changes occur in collisions with ground electronic state glyoxal. The study was made by examination of the rotational structure in the 5₁⁰ emission band at various pressures after excitation in the 0,0 band of the S₁—S₀ system with the 454.5 nm argon ion line.     

Charge transfer collisions between fullerenes: C 60 3+ + C60

Charge transfer collisions between C ₆₀ ³⁺ and C₆₀ are studied for collision energies between 400 and 3600 eV. Single and double electron transfers are observed, both occuring under single collision conditions. Absolute charge transfer cross sections are determined as a function of collision energy. The cross section for single electron capture of approx. 300 Ų is about two times larger than that for double electron transfer. For both processes the cross section increases slightly with increasing collision energy.     

Enhancement of two-photon absorption cross section and singlet-oxygen generation in porphyrin-cored star polymers

We report a newly synthesized polymer of a star-shaped porphyrin compound(TPA-FxP) with four oligofluorene arms at its meso positions with the pronounced enhancement of the two-photon properties and the generation of singlet oxygen by utilizing the two-photon excited fluorescence resonance energy transfer.The steady-state spectra and transient triplet-triplet absorption spectra give evidence that the enhanced two-photon absorption cross section results from not only the through-space energy transfer(Frster...     

Velocity dependence of vibrational branching ratios in electronic energy transfer collisions of metastable argon atoms with nitrogen

Measurements have been made of the vibrational branching ratio (υ′=0)/(υ′=1) in N^*₂ (C³Π_u) formed in electronic energy transfer collisions between argon metastable atoms and ground state nitrogen molecules, using crossed molecular beams. In the relative collision energy range, 0.08–0.20 eV, this ratio is 3.5±0.2.     

Collision spectroscopy with aligned and oriented atoms

Neutralisation processes in 0.15–1.5 keV collisions of H^? with Na atoms in the 3s ground state or in the excited 3p state have been investigated by means of time-of-flight analysis of the neutral H atoms produced. The H^? - Na(3p) system, investigated here for the first time, is particularly interesting since the entrance channel is embedded in the [H - Na(3s)] +e ^? continuum, enabling Penning detachment to occur. The measured relative neutralisation cross section ratios σ(3p)/σ(3s) decrease from 3 to 1.6 with increasing energy. Based on earlier published results for σ(3s), σ(3p) total cross sections exceeding 100 Ų are estimated.     

Excitation transfer in collisions of highly excited alkali atoms. Cesium-cesium collisions

Possible mechanisms of the resonance and near-resonance excitation transfer in collisions of Cs^**(8²P) with Cs(6²S) are discussed. Estimated cross section for the intramultiplet mixing is in close agreement with experimental results.     

Spin–orbit and dispersion energy effects in XeF

Spin–orbit and dispersion energy contributions to the energy curves of XeF are examined. A rapid variation in the spin–orbit coupling with internuclear separation is found for both the ground and excited states. This result can explain the experimentally observed ordering of the ionic excited states when the spin–orbit perturbation couples ²σ and ²π energy curves obtained by both all-electron and effective core potential (ECP ) calculations at the first-order configuration interaction (FOCI ) level of accuracy. Damped dispersion energy contributions to the ground-state energy curve are shown to be comparable to the charge transfer contribution. The energy curve for XeF is in reasonable agreement with experimental results and a calculation of the analogous XeCl curve confirms the qualitative correctness of the calculation. The energy curves and transition moments were then applied to two problems related to the efficiency of the XeF laser. Photodissociation of the X state provides a means of removing a bottlenecked vibrational level but a calculation of the radiative transition probability between the X and A states finds the cross section is too small to yield rates competitive with collisional deactivation. The bottlenecked state may also be removed by electron dissociative attachment but the calculated energy curves for the X states of XeF and XeF^? do not cross at a low energy indicating a small cross section.     

Collisional excitation transfer between lithium isotopes

Excitation transfer between the 3S _1/2 states of the lithium isotopes⁶Li and⁷Li is measured in a thermionic diode. The 3S level is excited by off-resonant two-photon transitions with a single mode ew laser. The relative densities of the directly excited and collisionally populated levels are probed by further laser excitation to the 12P levels. An energy transfer cross section of 585 Ų±160 Ų is found at the experimental temperature of about 850 K. A simple semiclassical calculation yields a cross section of 450 Ų.     

The collision cross sections for the fine-structure mixing of caesium 6P levels induced by collisions with potassium atoms

The cross section for the fine-structure excitation transfer Cs(6P _1/2) → Cs(6P _3/2), induced by collisions with the ground state potassium atoms, has been measured by resonant Doppler-free two-photon spectroscopy. The population densities of caesium 6P _J (J=1/2, 3/2) levels were probed by thermionic detection of the collisionally ionized caesium atoms from the Cs(6P _J ) → Cs(10S _1/2) excitation channel. The cross section for the transfer process at the temperatureT=503 K has been found to be σ(1/2 → 3/2)=45 Ų ± 20%. The result is compared with previously published experimental cross sections for fine-structure transfer in resonance states of other alkali elements perturbed by potassium and a thoeretical value of the Li(2P _J )-K system calculated in a simple approach.     

Resonance ionisation of Ga atoms

Saturation of the photoionisation of Ga atoms by resonance ionisation is demonstrated. The photoionisation cross section of the excited 4s²(1S)_3/2 state is measured to be 3 × 10^?18 cm². Saturation (100% ionisation) of a given samnple is achieved at power levels of the order of 100 MW/cm².     

1B2u1A1g fluorescence from benzene produced by electron impact (0–30 eV)

The ¹B_2u¹A_1g fluorescence of benzene resulting from the impact of low energy electrons (0–30 eV) has been studied in the pressure range 10^?4 ?2 × 10^?3 torr. It is found that the apparent emission cross section near threshold varies linearly with the pressure. A reaction scheme explaining this behaviour is given. From the absolute value of the apparent emission cross section it follows that excitation of the ³E_1u state is by far dominant over excitation of the ¹B_2u state at low electron impact energies.     

Electron-impact excitation of the 3s'3P° and 2s2p53P° autoionizing states of atomic oxygen

The excitation of the 3s''³P° and 2s2p⁵³P° autoionizing states of OI by electron impact on atomic oxygen has been studied. Absolute cross section values from threshold to 300 eV have been obtained for the 3s''³P° state. Limited emission cross section data for the 2s2p⁵³P° and other partially radiating autoionizing states were also obtained at an impact energy of 100 eV. These results suggest that the excitation of the OI autoionizing states account for ≈33% of the total O⁺ total ionization cross section at 40 eV under optically thin conditions and that the cross section ratio, σ(⁴S)/σ(²D + ²P), has been underestimated substantially in earlier theoretical work. Electron-impact excitation of the 3s''³P° and 2s2p⁵³P° states in an optically thick medium enhances the effective total ionization cross section for atomic oxygen by ≈15% and increases the specific O⁺(⁴S) production rate by ≈25% with important implications for O⁺ ion chemistry in gaseous discharges and planetary ionospheres.     

Fine structure excitation transfer between the lithiumD-lines by collisions with cesium atoms

Applying resonant Doppler-free 2-photon laser spectroscopy with thermionic diode detection, the cross sections for the excitation energy transfer of the collisional process⁷Li*(2P _1/2+Cs(6S _1/2)→⁷Li*(2P _3/2)+Cs(6S _1/2) have been measured. The experimental cross sections, σ^Li-Cs (1/2→3/2)=890 Ų and σ^Li-Cs (3/2→1/2)=430 Ų, are compared with theoretical data obtained by a sudden impact approximation approach taking into account the long-range interaction potentials only. The calculated cross sections show an excitation mixing process at large internuclear distances where Li-Cs dipole-dipole and dipole-quadrupole interaction forces are predominant.