Collisions of metastable Ne*, He* atoms with ground-state He,Ne atoms studied by atomic beam and laser techniques

A crossed nozzle-beam experiment is used to investigate thermal energy collisions: Ne*(2p ⁵3s,³ P _{0, 2})+He(1s ²,¹ S ₀), almost purely elastic, and He*(1s2s,^{1, 3} S)+Ne(2p ⁶,¹ S ₀), in which inelastic excitation transfers occur. State and velocity selection of the scattered Ne* atoms is performed using a tunablecw dye laser frequency locked on a definite Zeeman component of the transition 1s ₅→2p ₆ (λ=614.3 nm) of²⁰Ne or²²Ne. In the purely elastic case, this technique allows the selection of one of the two final velocities, and then an unambiguous LAB-CM transformation. The differential cross section at 62 meV tallies on accords with a calculation using a single effective potential. In He* on Ne collisions, the main inelastic processes are endothermic excitation transfers from He*(2¹ S). Experimental results obtained at different energies (62, 95, 109, 124 meV) show that the transfers essentially result in levels 3s and 4d of Ne.     

Electron transfer from laser excited rydberg atoms to molecules. Absolute rate constants at low and intermediate principal quantum numbers

Using mass spectrometric detection of positive and negative ions, we have investigated ionizing reactions of Ne(ns,nd) Rydberg atoms, efficiently excited by resonant two-photon excitation of metastable Ne(3s ³ P ₂) atoms, with electron attaching moleculesBC (BC=SF₆, CCl₄, CS₂, O₂) at thermal collision energies. Absolute rate constants have been determined in the range of low and intermediate principal quantum numbersn(5≦n?30) by utilizing the photoionization signal caused by room temperature black-body radiation and the loss of Ne(3s ³ P ₂) atoms, associated with the laser excitation. Substantially differentn-dependences of the electron transfer cross section have been found for the larger molecules (BC = SF₆, CCl₄) and the smaller molecules (BC = CS₂, O₂). Simple model calculations have been performed to gain new insight into the dynamics of the electron transfer process; forBC = SF₆, our results at lown(5 ≦n ≦ 10) suggest that internal energy conversion in the Coulombic complex Ne⁺ — SF ₆ ^? is important for the formation of the detected ions.     

Dielectronic recombination of lithium-like Ar15+

Dielectronic recombination (DR) of Ar¹⁵⁺(1s ²2s) ions was studied in a single-pass merged-beams experiment at the UNILAC (universal linear accelerator) of GSI. Absolute recombination rates and cross sections were measured for electron-ion center-of-mass energies from 0 to 580 eV. A number of Rydberg states formed by DR with 2s → 2p (Δn=0) and 2s → 3? (Δn=1) core excitations and even individual terms in the 1s ²3?3?′ configuration could be resolved. Theoretical calculations of DR cross sections are in good overall agreement with the data. In the calculations for Δn=0 transitions, effects of electric fields have to be included to reproduce the magnitude of the measured DR rates at the limit of the 2 _{p 1/2}? and 2 _{p 3/2}? Rydberg series. Discrepancies between theory and experiment are observed at the series limits of the (1s ²3?n?′) Rydberg series.     

The interaction of metastable Ne(3s 3 P 2,3 P 0) atoms with alkali atoms

Using crossed beams of alkali atoms (Li, Na, K) and state-selected metastable Ne(3s ³ P ₂,³ P ₀) atoms, we have measured the energy spectra of electrons resulting in the respective Penning ionization processes at thermal collision energies. The spectra are very different for Ne(³ P ₂) and Ne(³ P ₀): those for Ne(³ P ₂) are broad due to a strongly attractive interaction potential with a well depth of 798 (30) meV (Li), 672(20) meV (Na), and 561(20) meV (K), those for Ne(³ P ₀) are narrow and compatible with van der Waals type attraction (well depth <50 meV). The Ne(³ P ₂) cross section exceeds the one for Ne(³ P ₀) by about an order of magnitude.     

Rydberg spectra of bis(η-benzene)chromium derivatives: Gas-phase photoabsorption study of bis(η-1,2,4-trimethylbenzene)chromium and bis(η-1,2,4,5-tetramethylbenzene)chromium

The gas-phase electronic absorption spectra of (η⁶-1,2,4-C₆H₃Me₃)₂Cr (1) and (η⁶-1,2,4,5-C₆H₂Me₄)₂Cr (2) have been measured for the first time and compared with those recorded in n-pentane solution. The gas-phase spectra of both compounds show transitions from the non-bonding chromium 3d_z² orbital to molecular Rydberg s, p and d levels. The first ionisation potentials have been determined from the Rydberg frequencies as 4.994±0.009 and 4.862±0.009 eV for 1 and 2, respectively. Detailed assignments of Rydberg bands have been made on the basis of analysis of the quantum defects and term values. The Rydberg structures agree with the C₁, C_s or C₂ conformation for 1 and the D_2d geometry for 2 in the gas phase. In crystal, however, the molecule of 2 appears to adopt an eclipsed conformation close to D_2h as indicated by the X-ray diffraction. The influence of ring methylation on the Rydberg term values has been analysed for the first time.     

Penning ionization electron spectrometry of hydrogen iodide

The energy spectra of electrons released in thermal energy ionizing collisions of metastable helium and neon atoms with hydrogen iodide have been measured with high resolution and low background. The electron spectra, obtained for a mixed He(2¹ S, 2³ S) beam, a pure He(2³ S) beam, and a mixed Ne(3s ³ P ₂,³ P ₀) beam, are all characterized by the formation of theX ²Π _i andA ²Σ⁺ states of HI⁺. For both He(2¹ S) + HI and He(2³ S) + HI the spectra exhibit some broad features in the medium electron energy range which are attributed to ionization from an additional charge exchanged potential surface (He⁺ + HI^?) in the entrance channel. For the first time, we have detected the low energy electrons in the He(2¹ S, 2³ S) spectra due to autoionization of I** atoms which result from energy transfer to highly excited, dissociative HI** Rydberg states. The HI⁺ (X)²Π_3/2:²Π_1/2 fine-structure branching ratios vary significantly with the ionizing agent in a similar way as for the isoelectronic, atomic target case xenon.     

Thermal energy collisions between metastable Ne⋆(2p 53s,3 P 0, 2) and H2(X,1Σ g + )

A crossed beam experiment is used to investigate the Ne*(2p ⁵ 3s,³ P _{0, 2}) ? H₂(¹Σ _g ⁺ ) collision at thermal energy (67 meV). The H₂ beam is supersonic, the Ne* beam is thermal. Different collision processes have been analyzed separately by means of a double chopping technique combined with a time of flight measurement. Ions produced by Penning effect and chemi-ionization have been separated from scattered metastable atoms by an accelerating electric field small enough to preserve a reasonable angular resolution: δ?(ions)=±5.5°, δ?(Ne*)=±1°, which allows a determination of differential cross sections. The attenuation method, combined with an absolute measurement of the total H₂ flux, has been used to measure the total cross section: σ _t =940±220a ₀ ² . Differential cross sections have been obtained, in arbitrary but unique unit, for the following processes: (1) elastic collisions, for a mixture (1:3) of para- and ortho-hydrogen; (2) rotationally inelastic collisions:J=0→2; (3) Penning ionization resulting into H ₂ ⁺ ions; (4) chemiionization yielding NeH⁺ ions.     

The state dependence of the interaction of metastable rare gas atoms Rg*(ms3 P 2,3 P 0) (Rg=Ne,Ar, Kr,Xe) with ground state sodium atoms

Using crossed beams of metastable rare gas atoms Rg*(ms³ P ₂,³ P ₀) (Rg=Ne, Ar, Kr, Xe) and ground state sodium atoms Na(3s ² S _1/2), we have measured the energy spectra of electrons released in the respective Penning ionization processes at thermal collision energies. For Rg*(³ P ₂)+Na(3s), the spectra are quite similar for the different rare gases, both in width and shape; they reflect attractive interactions in the entrance channel with well depthsD* _e [meV] decreasing slowly from Rg=Ne to Xe as follows: 676(18); 602(23); 565(26); 555(30). For Rg*(³ P ₀)+Na(3s), the spectra vary strongly with the rare gas, indicating a change in the character of the interaction from van der Waals type attraction (Ne) to chemical binding for Kr and Xe with well depthsD* _e [meV] of: 51(19); 107(25); 432(30); 530(50). These findings are explained through model calculations of the respective potential curves, in which the exchange and the spin orbit interaction in the excited rare gas and the molecular interaction between the two valences-electrons in terms of suitably chosen singlet and triplet potentials are taken into account. These calculations also explain qualitatively the experimental finding that the ratiosq ₂/q ₀ of the ionization cross sections for Rg*(³ P ₂)+Na and Rg*(³ P ₀)+Na vary strongly with the rare gas from Ne to Xe as follows: 15.8(3.2); 2.6(4); 1.4(2); 1.6(4).     

Oscillator strength measurements of the 5s5p 3P1 → 5snd 3D2 Rydberg transitions of cadmium

We report oscillator strengths distribution in the bound region of cadmium corresponding to the 5s5p ³P₁ → 5snd ³D₂ (21 ≤ n ≤ 52) Rydberg transitions. The experiment was performed using two frequency doubled dye lasers simultaneously pumped by a common Nd:YAG laser in conjunction with an atomic beam set-up. The absolute photoionization cross section of the 5s5p ³P₁ intermediate state at the 5s ²S_1/2 ionization threshold has been measured as 20 (4) Mb using the saturation technique. The measured value of the photoionization cross section at threshold is used to extract the f-values of the above mentioned Rydberg transitions.     

Theoretical studies of photodissociation and rydbergization in the first triplet state (3s3A″2) of ammonia

Ab initio investigations at the RHF and CI levels have been carried out on a section of the potential energy surface of the Rydberg 3s³A″₂ state of NH₃ leading to dissociation into NH₂(²B₁) and H(²S). It was found that the barrier towards dissociation is due to a Rydberg-valence transformation. The barrier height calculated with the CI wavefunction is significantly smaller than at the RHF level The results may explain the difficulties associated with experimental observation of the 3s³A″₂ state.     

Quantum chemical ab initio calculations for excited states of F IV

Quantum chemical ab initio calculations have been performed for the ground state and for several excited states of the F³⁺ ion (F IV). Three levels of accuracy have been used: Frozen-core SCF calculations (FRC-SCF) to determine orbital energies ε _nl and quantum defects δ _l for excited Rydberg orbitalsnl; frozen-core SCF followed by CI calculations (FRC-CI) which account for multiplet splittings and configuration mixings, and multi-configuration coupled-electron-pair approximation (MC-CEPA) calculations which include dynamic correlation effects. The accuracy of the calculated excitation energies is in the order of 5000 cm^?1 at the FRC-CI level and in the order of 500 cm^?1 at the MC-CEPA level. This latter error amounts to about 0.1% for excitation energies in the range of 400000 to 600000 cm^?1. The MC-CEPA calculations have been performed for 17 experimentally known states and for 14 experimentally unknown states, in particular for the configurations 2s2p ² (² D)3s, 2s 2p ²(² S)3s, 2s ² 2p 4p, and 2s ² 2p 5p.     

Collisional de-excitation of the metastableD-states of Ba+ by He,Ne, N2 and H2

The rate constants 〈σ · υ〉 for collisional de-excitation of the metastable 5D states of Ba⁺ ions have been determined in an ion trap experiment. TheD-states are selectively populated by pulsed laser excitation of the 6P _1/2 or 6P _3/2 state and the decay at different background pressures is monitored by the change in fluorescence intensity of the excited ions. From the pressure dependence of the decay constants we calculate the de-excitation rate constants for different collision partners, averaged over the velocity distribution of the trapped ion cloud. For He, Ne, H₂ and N₂ we obtain in the c.m. energy range of 0.1–0.5 eV: 〈σ·υ〉 (He)=3.0±0.2·10^?13cm³/s, 〈σ·υ〉 (Ne)=5.1±0.4·10^?13cm³/s, 〈σ·υ〉 (H₂)=3.7±0.3·10^?11cm³/s, 〈σ·υ〉 (N₂)=4.4±0.3·10^?11cm³/s. The results can be understood qualitatively by a consideration of the ion-atom and ion-molecules interaction potential.     

Stark broadening and regularities of ionized neon and argon spectral lines

Stark widths of five Ne III, five Ne IV, one Ar III and nine ArIV spectral lines have been measured in a linear-pinch discharge plasma. The results were compared with existing experimental and theoretical results, and used to establish several types of regularities. Electron densities determined with single-wavelength laser interferometry were 2.18·10²³ m^?3 and 2.80·10²³ m^?3 in neon and argon plasma, respectively. The electron temperatures determined from the Boltzmann slope of several Ne III spectral lines, and ratios of Ne III to Ne IV or Ar III to Ar IV spectral lines were 59 000 K and 42 000 K in neon and argon plasma, respectively. The investigated spectral lines originate predominantly, from 3s–3p and 3s′–3p′ Ne III and Ne IV, and from 4s–4p and 4s′–4p′ Ar III and Ar IV transition arrays. The emphasis is on the Stark width (θ) dependence on the upper level ionization potential (I), the emitter core net charge (z) and electron temperature (T) for a given electron density. This dependence was found to be of the form: θ=az ² T ^?1/2 I ^?b , wherea andb are constants within(i) several stages of ionization of neon or argon and(ii) within nitrogen like (NI, O II, F III and Ne IV) 3s–3p or phosphorus like (P I, S II, Cl III and Ar IV) 4s–4p transition arrays. The established overall trends were used to predict the Stark widths of univestigated spectral lines originating from the given transition arrays.     

Stark manifolds of barium Rydberg states

In a CW laser-atomic beam experiment Stark manifolds in barium originating from the Rydberg states 6s40f ¹ F ₃, 6s40g ^1,3 G ₄,³ G ₅ and 6s40h ^1,3 H ₅ have been studied. Accurate quantum defect values for higher orbital angular momentum states (l=6, 7) have been determined. The Stark manifolds are also calculated by diagonalization of the energy matrix in the presence of an external electric field. Good agreement between experiment and calculations is obtained.     

Formation of negatively-charged cluster ions in thermal energy collisions with state-selected rydberg atoms

Using crossed atomic, molecular cluster, and cw laser beams in conjunction with mass spectrometric ion detection, we have obtained for the first time results for electron transfer fromstate-selected Rydberg atoms to molecular clusters. We report negative ion mass spectra for (CO₂) _k ^? (4≦k≦25) and (O₂) _k ^? (1≦k≦13) cluster ions, resulting from collisions of Ar** (nd) Rydberg atoms (12≦n≦40) with (CO₂) _m and (O₂) _m clusters at relative velocities around 830 m/s, and, for comparison, positive ion mass spectra due to Ne(3s ³ P _{2, 0}) Penning ionization. For both CO ₂ ^? and O₂-clusters, the negative and the positive ion mass spectra are very different. For (CO₂) _k ^Emphasis>/? cluster ions, the mass spectra show distinct variations with principal quantum number of the Rydberg atom, corresponding to differentn-dependences of the effective rate constant for selected cluster ions, as measured relative to the knownn-dependence for SF ₆ ^? formation in collisions with SF₆. For (O₂) _k ^? cluster ions, on the other hand, the mass spectra are almost independent ofn with ion intensities, which clearly reflect their thermochemical stabilities (O ₄ ^? as dominant species).     

Accurate comparison of Hel,NeI photoionization and He(23, 1 S), Ne(3s 3 P s,3 P 0) penning ionization of argon atoms and dimers

Using crossed beams and mass spectrometric ion detection, we have investigated the ionization of argon atoms and dimers in a skimmed supersonic beam by HeI (58.4 nm) and NeI (73.6, 74.4 nm) photons and by He(2^3,1 S) and state selected Ne(3s ³ P ₂,³ P ₀) metastable atoms. The cross section ratioq ₂₂/q ₁ (i.e. the cross sectionq ₂₂ for formation of Ar ₂ ⁺ ions from Ar₂ divided by the total ionization cross sectionq ₁ for Ar atoms), arbitrarily normalized to 1 for HeI impact, is found to vary weakly as follows: HeI/NeI/He(2^{3, 1} S)/Ne(³ P ₀)Ne(³ P ₂)=1/1.136(9)/0.893(4)/1.034(12)/0.985(9). The results are qualitatively interpreted using available information on the intermolecular potentials and the two different ionization processes. The observation thatq ₂₂/q ₁ is 5% larger for Ne(³ P ₀) than for Ne(³ P ₂) is attributed to anomalies in the respective branching ratios for formation of the Ar+(² P _3/2)/Ar⁺(² P _1/2) ion states in conjunction with differences in the stability of the formed Ar-Ar⁺(² P _3/2) and Ar-Ar⁺(² P _1/2) molecular ions.     

Partial differential cross sections for inelastic He++Ne collisions at low energy

We report differential cross section measurements with high angular resolution for different channels of the inelastic processes He⁺+Ne→He⁺+Ne* and He⁺+Ne→He*+Ne⁺, for collision energies between 100 and 200 eV. For the Ne states (2p ⁵3s)^1,3 P ₁, which decay optically, we determined the fraction with the alignment at right angles to the scattering plane. The results are used to discuss the mechanism of the processes and the influence of the spin-orbit interaction upon the collision.     

Penning ionization and photoionization electron spectrometry of hydrogen bromide

An electron spectrometric study has been performed on HBr using metastable helium and neon atoms as well as helium resonance photons. High resolution electron spectra were obtained for a mixed He(2¹ S, 2³ S) beam, a pure He(2³ S) beam, a mixed Ne(3s ³ P ₂,³ P ₀) beam, and for HeI VUV light. From the comparison of vibrational populations of HBr⁺ (X, v′) and HBr⁺ (A, v′), formed by either He^* and Ne^* Penning ionization (PI) or HeI photoionization, we conclude that HBr⁺ (X) formation by PI exhibits only little perturbation of HBr potentials, whereas HBr⁺ (A) formation by PI exhibits substantial bond stretching of HBr due to metastable atom attack preferably from the H end. For He(2¹ S) + HBr theX- andA-state vibrational peak shapes are substantially broader than for the He(2³ S) + HBr case pointing to an additional, charge exchanged interaction (He⁺ + HBr^?) in the entrance channel of the former system which is also responsible for a broad feature found at lower electron energies in the He(2¹ S, 2³ S) induced PI electron spectra. For the first time, we have detected the low energy electrons in both the He(2¹ S) + HBr and He(2³ S) + HBr spectra, associated with the major mechanism for the formation of Br⁺ ions: energy transfer to repulsive HBr** Rydberg states, dissociating to H(1s) and autoionizing Br** atoms. The HBr⁺ (X)² II _3/2:² II _1/2 fine structure branching ratios vary significantly with the ionizing agent in a similar way as for the isoelectronic, atomic target case krypton.     

Avoided level crossings in bound Rydberg states of barium in an electric field

In a CW laser experiment on bound Rydberg states of barium electric-field-induced level crossings were studied. A regular type of avoided crossing of 6snf ³ F ₂ and 6s (n+4)s ³ S ₁ levels (n≈60,M=0) was observed under circumstances where the minimum separation was larger than the linewidth involved. This type of crossing could be reproduced using a diagonalisation procedure of the total energy matrix in the presence of the field. However, in the case of avoided crossings of the 6snf ³ F ₂ and 6s(n+4)p ¹ P ₁ sublevels, where the minimum separation was smaller than the linewidth of the³ F ₂ level, an interference-like profile was recorded. An important feature in the explanation of this interference-like profile turned out to be the broadening of the³ F ₂ level by small field inhomogeneities.     

Case studies in multiphoton ionisation and dissociation of Na2

Dissociative ionisation of Na₂ via the 3s 3d ¹Σ _g and¹Π _g states has been studied in the near threshold energy regime up to 120 meV above the three particle (Na⁺ + Na(3s) +e ^?) break up limit. A pulsed, cold molecular beam, pulsed laser 2 colour 3 photon resonantly enhanced multiphoton ionisation, and kinetic energy analysis of the fragments by a time of flight method (KETOF) is used. As series of vibrational levels in the two intermediate 3s 3d Rydberg states are excited, slow Na⁺ fragments are observed with a maximum kinetic energy given by the excess energy of the 2 + 1 photon process above threshold, thus confirming a direct dissociative ionisation process. The intensity distribution of the Na⁺ fragments shows a very pronounced maximum at zero kinetic energy, its shape differing somewhat for the¹Σ _g and¹Π _g intermediate states. Also observed is a strong signal of fast fragments arising from a typical 4 photon process which leads to dissociation of Na ₂ ⁺ molecules in their electronic ground state.