Reactions of excited atoms and molecules with atoms and molecules

From a He-beam excited by electron impact we eliminated the He(2¹ S) component to better than 0.5% by irradiating light from a He discharge. The quenching process ishv(2¹ P→2¹ S)+He(2¹ S)→He(2¹ P)→He(1¹ S +hv) (2¹ P 1)¹ S. By measuring the ions produced in collisions of the He-metastables with various target gases in a mass spectrometer, singlet to triplet Penning-cross section ratios were obtained. These ratios are without exception close to one, which is taken as evidence for the previously proposed electron exchange mechanism of the Penning ionization. In the case that more ions are produced in the collision of He (2¹ S) and He(2³ S) with a target gas, separate relative production cross sections are obtained for the two metastables. For the rare gases the measurements are performed at two temperatures of the He-beam, 320 and 90 °K. It is found that the cross section ratio of associative — to Penning ionization increases considerably as the temperature is decreased for both, He(2¹ S) and He(2³ S), the effect being much more pronounced for He(2¹ S). The results of this work are found to confirm conclusions drawn from measured energy distributions of the electrons ejected in the Penning process.     

The temperature dependence of penning ionization electron energy spectra: He(23S)—ar,N2, NO,O2, N2O,CO2

Using two intense thermal energy He(2³S) sources of different temperatures (≈400 and ≈ 1000 K, resp.) and a transmission-calibrated electron energy analyzer with about 30meV resolution, the dependence of He(2³S) Penning ionization electron spectra on collision energy for the target species Ar, N₂, NO, O₂, N₂O and CO₂ have been studied. The energy shifts of the Penning electron energy distributions and the branching ratios for the population of different electronic states in the molecular ions are determined quantitatively and compared for the two different collision temperatures. These results and the shapes of the observed Penning electron energy distributions are discussed in the light of current models for the Penning procen; the observed temperature dependences are correlated with the nature of the ionized orbitals in cases of only one entrance channel (closed shell targets) and, in addition, to the existence of qualitatively different entrance channels (open shell targets).     

Electron spectroscopy using excited atoms and photons IV. Penning ionization of ethylene

Using helium metastable atoms (2¹S, 2³S), the Penning ionization of C₂H₄ has been studied using a high resolution electrostatic electron analyzer. The Franck—Condon envelope for the ground state of C₂H₄⁺ (X²B_3u) is found to be the same for He* (2³S) Penning ionization and 584 Å photoionization. The ΔE shift values and the relative electronic transition probabilities are reported for four ionic states. Unusually large differences have been found for the relative electronic transition probabilities for Penning ionization and photoionization.     

Comparative study of He(23S)-penning ionization and He(I) photoionization of CF4, CCl4, and the chlorofluoromethanes by electron-ion coincidence spectroscopy

We present electron—ion coincidence spectra of the chlorofluoromethanes obtained after He(I)-photoionization and Penning ionization by He(2³S).Remarkable differences between both modes of ionization exist for CF₃Cl. Our tentative interpretation suggests the existence of a strongly bound interaction potential of ionic character between He(2³S) and CF₃Cl, in addition to the essentially flat covalent potential.     

Electron spectrometry study of associative and penning ionization in laser excited sodium vapor

The first observation, by electron spectrometry, is reported in laser-excited sodium vapor of the primary low energy electrons produced by associative ionization and by Penning ionization of sodium atoms in highly excited n1 states. The sequential heating of these primary electrons has been observed in 1, 2 or 3 superelastic collisions with Na(3p) atoms. The variation of associative ionization was measured as a function of the excited state density by using inner-shell photoionization produced by synchrotron radiation. Finally, an associative ionization cross section of 3.8 X 10^-17 cm² and a Penning ionization cross section for the 5s state of 1.1 X 10^-12 cm² were found (within 50% uncertainty) for an oven temperature of 520 K.     

Velocity dependence of total Penning ionization cross sections

The velocity dependence of the total Penning ionization cross sections,σ(v), is measured in the thermal relative velocity region, using a time of flight method.σ(v) curves are reported for the collision systems He(2¹ S)/Ar, Kr, Xe, N₂, Hg, He(2³ S)/Ar, Kr, Xe, N₂, Hg, Ne(³ P _{2, 0})/Kr, Hg, and Ar(³ P _{2, 0})/Hg. In a qualitative discussion it is shown that all features of the measuredσ(v) curves may be explained within the frame of the theory of Penning ionization, allowing to extract information on the physical quantities governing the process: on the interaction potentialV(R) and on the transition probabilityW(R). A theoretical calculation for the He(2³ S)/Ar system shows good agreement with our experimentalσ(v) curve. On the basis of the present results earlier data onσ(v), and on absolute cross sections and rate constants obtained at certain relative velocity distributions are discussed.     

A Clear Atomic Example for the Surface Sensitivity of Penning Ionization: He*(23S) + Yb

Using a crossed-beam apparatus with a double hemispherical electron spectrometer, we have studied the spectrum of electrons released in thermal energy ionizing collisions of metastable He*(2³S) atoms with ground state Yb(4f¹⁴ 6s^{2 1}S₀) atoms, thereby providing the first Penning electron spectrum of an atomic target with 4f-electrons. In contrast to the Hel (58.4 nm) and NeI (73.6/74.4 nm) photoelectron spectra of Yb, which show mainly 4f- and 6s-electron emission in about a 5:1 ratio, the He*(2³S) Penning electron spectrum is dominated by 6s-ionization, accompanied by some correlation-induced 6p-emission (8% Yb⁺(4f¹⁴ 6p ²P) formation) and very little 4f-ionization (?2.5%). This astounding result is attributed to the electron exchange mechanism for He*(2³S) ionization and reflects the poor overlap of the target 4f-electron wavefunction with the 1s-hole of He*(2³S), as discussed on the basis of Dirac-Fock wave functions for the Yb orbitals and through calculations of the partial ionization cross sections involving semiempirical complex potentials. The presented case may be regarded as the clearest atomic example for the surface sensitivity of He*(2³S) Penning ionization observed so far.     

Electron spectroscopy using excited atoms and photons: II. Penning ionization of diatomic molecules

A high resolution electrostatic electron analyser has been used to study Penning ionization electron spectra of H₂, HD, D₂, N₂, CO, NO and O₂ using helium metastable atoms (2¹S, 2³S). Results for H₂, N₂ and CO are in good agreement with other work. New data are presented for HD, D₂, NO and O₂. The Penning electron spectra are also compared to the 584 Å photoelectron spectra obtained in the same apparatus. The relative vibrational intensifies for the given electronic bands indicate that in most cases Franck—Condon factors for Penning ionization and photoionization are very similar. However for the O₂⁺(X²Π_g) band, the (2³S) Penning electron and photoelectron spectra show significant differences in the Franck—Condon envelopes This perturbation of the envelope for the Penning ionization may be explained by a competing autoionization process. The relative electronic transition probabilities are in many cases found to be different for Penning ionization and photoionization.     

Two-dimensional Penning ionization electron spectroscopic study on outer characteristics of molecules

Collision-energy/electron-energy-resolved two-dimensional Penning ionization electron spectroscopy (2D-PIES) has been used to study outer characteristics of molecules. Anisotropic potential energy surfaces for collisional ionization of molecules with a metastable helium atom He*(2³S) have been determined starting from ab initio model potentials via optimization based on trajectory calculations. Since ionization widths in the theoretical model of Penning ionization are functionals of target molecular orbitals, outer electron distributions of molecular orbitals can be determined via optimization procedures of calculated ionization cross-sections by trajectory calculations with respect to observed 2D-PIES data.     

Elastic scattering of metastable He(21,3 S) atoms by Na(32 S) atoms at 68 meV

The spectroscopy of metastable states is used to make the first experimental measurement of the total differential elastic-scattering cross sections of metastable helium atoms in 2³ S and 2¹ S states by sodium atoms in the ground state at interaction energy 68 meV in the center-of-mass system. To analyze the experimental data, the partial scattering phases are calculated using the method of phase functions in the optical potential approximation. The analysis makes it possible to give a more detailed interpretation of the structure of the differential cross section. The computed integral cross sections, specifically, Penning ionization, diffusion, viscosity, and spin exchange are discussed.     

Electron spectroscopy using excited atoms and photons IX. Penning ionization of CO2, CS2, COS,N2O,H2S,SO2, and NO2

The electron spectra resulting from thermal collisions of He* (predominantly 2³S) metastable atoms with the seven triatomic molecules, CO₂, COS, CS², N₂O H₂S, SO₂ and NO₂, are compared with their respective 584-Å photoelectron spectra using a transmission-corrected electron spectrometer. The normalised relative electronic-state transition probabilities for production of ionic states in Penning ionization and photoionization are reported together with energy shifts (ΔE values) for He*(2³S) Penning ionization. The cross-section for Penning ionization to lower states of NO₂⁺ is extremely low as has been observed in other open shell molecules such as NO and O₂.     

Electron spectroscopy using excited atoms and photons VI. Penning ionization of HCN and some related compounds

The He*(2¹S, 2³S) Penning ionization electron spectra of HCN, (CN)₂, CH₃CN, BrCN and ICN are compared to the corresponding 584 Å photoelectron spectra. Large differences are observed for the relative populations of the ionic states of the various molecules when Penning ionization is compared to photoionization. For these molecules, the ratio of the normalized relative populations of states corresponding to removal of π bonding and nitrogen lone pair electrons is significantly greater for 584 Å photoionization than for He*(2³S) Penning ionization. Some unidentified chemi-ionization processes are observed for (CN)₂, BrCN and ICN.     

Ionization of O2 by metastable He(23 S, 21 S) at thermal collision energy

We investigate Penning ionization of O₂ by He(2³ S, 2¹ S) by means of electron spectroscopy. We give a detailed analysis of the reaction mechanism which completes and partly corrects earlier interpretations given by other authors. It becomes apparent that symmetry properties of the reaction partners play an important role.     

Chemical ionization of hydrogen halide molecules in collision with metastable helium atoms

An anomaly of the temperature dependence of the cross section for chemical ionization of HBr molecules by metastable helium atoms He*(2³ S ₁) is discovered. It is shown that the interaction anisotropy induced by rotation of the HBr molecule has a significant influence on the formation of the anomaly. Zh. Tekh. Fiz. 68, 13–15 (February 1998)     

Subject index

We have investigated the Penning ionization of NO₂(²A₁) by He(2³S) by means of electron—ion coincidence measurements. It is possible to identify two entrance channels. The quartet state is essentially repulsive and gives rise to an electron energy spectrum similar to that found in photoionization. The doublet entrance channel is strongly attractive with a well depth D_e of 4.8 {_?0.3^+0.1 eV. Ionization out of this channel leads to very broad features in the electron energy spectrum.     

Electron spectroscopy of surfaces by impact of metastable He atoms: CO on Pd(110)

Deexcitation of metastable He1 2¹S (excitation energy E1 = 20.6 eV) or 2³S (E* =19.8 eV) atoms at a clean Pd(110) surface proceeds through a two-stage process (resonance ionization + Auger neutralization, RI + AN). The measured electron energy distribution reflects the self-convolution of the local density of states of the outmost atomic layer. A CO adlayer suppresses the RI step and the spectra are caused by Auger deexcitation (Penning ionization). Comparison with corresponding UPS data allows identification of the valence orbitals of the adsorbate. Emission up to the Fermi level is ascribed to contributions from the 5σ level. The effectively available excitation energy in front of the adlayer is lowered by 0.5 eV. Extensive data on the variation of the intensities from the adsorbate valence levels with angle of incidence as well as of emission are presented and are analyzed in terms of an empirical model.     

(e, 3e) Differential cross section of He (21 S) and He (23 S)

The angular distribution of the five-fold differential cross section for the electron impact double ionization of He (2¹ S) and He (2³ S) has been studied. The kinematical conditions for maxima/minima in the angular distribution for the two cases have been compared. The two-step process for the double ionization is found to contribute very little in the triplet case.     

Collision-energy-resolved Penning ionization electron spectroscopy of styrene, 2-vinylpyridine, and 4-vinylpyridine with He*(23S) metastable atoms

Collisional ionization of styrene (phenylethylene), 2-vinylpyridine, and 4-vinylpyridine with metastable He*(2³S) atoms were studied by means of collision-energy/electron-energy resolved two-dimensional Penning ionization electron spectroscopy. Collision energy dependence of partial ionization cross-sections, which reflects the anisotropic interactions between a He*(2³S) atom and the target molecules, indicates that attractive interaction for the out-of-plane access of a He*(2³S) atom to phenyl group is stronger than that for the out-of-plane access to vinyl group. Moreover, it was found for vinylpyridines that the attractive interaction around π electrons became weaker than that for styrene, and that the attractive interaction for the in-plane access to the nitrogen atom is stronger than that for out-of-plane π-directions. However, in 2-vinylpyridine, the hydrogen atom of vinyl group prevents a He*(2³S) atom from approaching to the nitrogen atom along in-plane directions, and thus the attractive interactions around the nitrogen atom were shielded by the vinyl group. The experimentally observed anisotropic interactions were qualitatively supported with ab initio model interaction potential calculations between a Li (He*(2³S)) atom and the target molecule. Concerning with electronic structures of investigated molecules, the assignment of Penning ionization electron spectrum for 4-vinylpyridine was discussed on the basis of different behavior of collision-energy dependence of partial ionization cross-sections, and the satellite ionization band in Penning ionization electron spectra was also reported for styrene.     

Measurement of the spin-exchange and chemical ionization rate constants in collisions of polarized metastable 23 S 1 helium atoms with 32 S 1/2 sodium atoms

Experimental data on the spin-exchange rate constants for the He(2³ S ₁)-Na(3² S _1/2) system are reported for the first time. Measurements show that the spin-exchange rate constant is C _se = (23 ± 11) × 10⁻¹⁰ cm³ s⁻¹ and the chemical ionization rate constant is C _si = (29 ± 14) × 10⁻¹⁰ cm³ s⁻¹ at a temperature of 420 K. The results are compared with the data calculated from the rate constants.     

Photoelectron and Penning ionization electron spectrometry with a differential retarding field analyzer

A differential retarding field analyzer of the type described by Lindau et al.² has been tested in detail by photoelectron spectrometry in the 0–10-eV range. A resolution of 17 meV was obtained together with a satisfactory line-shape and sensitivity. The important potential parameters concerning resolution and line-shape, and the energy-dependence of the transmission of the analyzer have been determined experimentally. As a first application, Penning ionization electron spectra for the systems He(2³S)-N₂ O₂, and HCl have been obtained with the transmission-calibrated analyzer.