Decay reactions of rare gas cluster ions: Kinetic energy release distributions and binding energies

We have carried out measurements on metastable fragmentation of mass selected argon cluster ions which are produced by electron impact ionization of a neutral argon cluster beam. From the shape of the fragment ion peaks (MIKE scan technique) one can deduce information about the distribution of kinetic energy that is released in the decay reaction. In this study, for Ar ₅ ⁺ to Ar ₁₅ ⁺, it is Gaussian and thus we can calculate from the peak width the mean kinetic energy release 〈KER〉 of the corresponding decay reactions. Using finite heat bath theory we calculate from these data the binding energies of the decaying cluster ions. Received 20 November 2000     

Recombination measurements at low energies with Ar16+ and Ar18+ ions in a dense, cold electron target

Recombination of multiply charged ions with electrons at very low relative energies has become a major topic of interest, due to the observation of rates which are enhanced beyond the expectations for radiative recombination. We present results for Ar¹⁶⁺ and Ar¹⁸⁺ ions from systematic measurements along the argon isonuclear sequence using a high density cold electron beam target (n_e = 7 × 10⁹ cm^-3) at the UNILAC of GSI. The transverse and longitudinal temperatures of the electron beam were determined from DR resonance features observed with metastable Ar¹⁶⁺ (2³S) ions. The rate at E_rel = 0 for radiative recombination of completely stripped Ar¹⁸⁺ calculated with electron beam temperatures kT_∥ = 0.002 eV, kT_⊥ = 0.2 eV amounts to α = 10^-9 cm³ s^-1. This is exceeded by nearly a factor of 10 by the rate measured in experiments with Ar¹⁸⁺ ions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preferential sputtering of TIC under keV Ar+ ion bombardment: Simultaneous sputtering-ISS measurement with He+ and Ar+ ions

The composition change of the outermost atom layer of TiC(110) under ion bombardment with 1.5–3 keV He⁺ and He⁺ + Ar⁺ ions has been measured by ion scattering spectroscopy with He⁺ ions at different sample temperatures. It has been found that the preferential sputtering of C atoms takes place for both the He⁺ and Ar⁺ ion bombardment, however the preferred sputtering is more pronounced for Ar⁺ ions than for He⁺ ions. The ion bombardment with He⁺ ions at elevated sample temperatures hardly results in any change in surface composition below ～800°C, while Ar⁺ ion bombardment results in C enrichment for elevated temperatures as reported so far.     

L α emission from Ar++H2 collisions in the threshold energy region

In the energy range 2.4 to 33.3 eV_CM, relative cross sections have been measured forL _α emission from impact of Ar⁺ ions in a beam on a H₂ gas target. Absolute cross sections, obtained by normalization to literature data, are 1–10×10^?16cm² for metastable Ar⁺ and 1–20×10^?18cm² for ground state Ar⁺. In the former case, the dominant mechanism is probably dissociative electronic energy transfer, while in the latter case dissociative charge transfer is the most likely process. In addition, at the lowest energiesL _α resulting from a chemiluminescent rearrangement Ar⁺+H₂→ArH⁺+H(2p) has been observed.     

Isotope effects in the metastable decay of Ne2 +

Neon dimer ions undergo spontaneous dissociation (metastable decay) several microseconds after formation by electron impact ionization of neon clusters. In this contribution we compare the kinetic energy release distribution (KERD) of the previously reported isotopomer ²⁰Ne₂ ⁺ with that of ²²Ne₂ ⁺. The heavy isotopomer shows the same two components in the KERD as the lighter ones. However, the high-energy component that is due to electronic pre-dissociation is reduced in intensity. The decrease is attributed to a reduced predissociation rate from the II(1/2u) state into I(3/2u).     

High resolution spectroscopy of prompt and metastable decaying levels in highly ionized argon,especially of the metastable3 P 2-state of Ar16+ and the4 P 5/2-state of Ar15+

Besides the prompt x-ray emission of Ar-ions, the metastable decay of the heliumlike³ P ₂- and the lithiumlike⁴ P _5/2-levels of highly ionized Ar¹⁶⁺ and Ar¹⁵⁺ atoms has been observed in a foil-excited beam using a flat-crystal spectrometer. Due to the highx-ray energy resolution of the spectrometer the two³ P ₂ →¹ S ₀ and⁴ P _5/2 →² S _1/2 transitions could be resolved. The experiment yielded (3128 ±2) eV for the³P₂ → and (3091 ± 2)eV for the⁴ P _5/2 →² S _1/2 transition energy respectively. Using a time of flight technique the lifetimes of the³ P ₂- and the⁴ P _5/2-states were determined to be (1.44 ±0.09)ns and (0.66 ± 0.05) ns.     

Effect of helium/argon gas ratio in a He-Ar-Cu<Superscript>+</Superscript> IR hollow-cathode discharge laser: modeling study and comparison with experiments

The He-Ar-Cu⁺ IR laser operates in a hollow-cathode discharge, typically in a mixture of helium with a few-% Ar. The population inversion of the Cu⁺ ion levels, responsible for laser action, is attributed to asymmetric charge transfer between He⁺ ions and sputtered Cu atoms. The Ar gas is added to promote sputtering of the Cu cathode. In this paper, a hybrid modeling network consisting of several different models for the various plasma species present in a He-Ar-Cu hollow-cathode discharge is applied to investigate the effect of Ar concentration in the gas mixture on the discharge behavior, and to find the optimum He/Ar gas ratio for laser operation. It is found that the densities of electrons, Ar⁺ ions, Ar_m ^* metastable atoms, sputtered Cu atoms and Cu⁺ ions increase upon the addition of more Ar gas, whereas the densities of He⁺ ions, He₂ ⁺ ions and He_m ^* metastable atoms drop considerably. The product of the calculated Cu atom and He⁺ ion densities, which determines the production rate of the upper laser levels, and hence probably also the laser output power, is found to reach a maximum around 1–5 % Ar addition. This calculation result is compared to experimental measurements, and reasonable agreement has been reached. Received: 14 October 2002 / Revised version: 28 November 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +32-3/820-23-76, E-mail: annemie.bogaerts@ua.ac.be     

极板电压与间距对大气压射频氩等离子体放电参数的影响

 基于1维流体力学模型,对大气压射频裸露金属电极氩气放电过程进行了研究。模型中考虑了氩等离子体放电过程中主要发生的激发和电离等7个反应过程,对等离子体反应产生的主要粒子,包括电子、氩原子离子Ar⁺、氩分子离子Ar2⁺和氩激发态Ar^*等,建立连续性方程、动量方程和电流平衡方程。分析了极板电压、极板间距对上述粒子数密度分布的影响。给出了电子,Ar⁺,Ar^*和Ar₂⁺密度随极板电压及间距变化的时空演化过程。得出极板电压或极板间距的改变会使放电空间的电场发生改变,对应一定的极板间距,极板电压有一个最佳值,极板电压和间距的变化会使对应的极板间有一个最佳电场值,而对应最佳电场有一个等离子体气体间最佳反应系数,从而使放电空间粒子数密度发生改变。     

Exploration of large amplitude motions in the Ca+Ar2 complex

ABSTRACT

We present a theoretical study of the ground electronic state potential of the Ca⁺Ar₂ complex and of its photoabsorption spectra, simulated at temperatures ranging between 20 and 220?K. These calculations exploit a Monte-Carlo (MC) method, based on a one-electron pseudo-potential approach. A pairwise additive potential fitted to coupled cluster ab initio points, is used to model the Ca⁺Ar₂ complex. Our study shows that the most stable form of Ca⁺Ar₂ is a bent C_2v structure, whereas the linear isomer is located at around 90?±?10?cm^?1 above in energy. The analysis of the photoabsorption spectra establishes that a structural transition from bent Ca⁺Ar₂ to linear ArCa⁺Ar occurs at T～100?K. Trends in binding energies of both isomers, bond lengths and bond angles are also discussed. Molecular orbital overlaps provide an explanation for the order of stability between the bent and linear structures.     

Dissociation energies of the I(3/2g) and I(1/2g) states of Ar+ 2

Rotationally resolved pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectra of ⁴⁰Ar₂ and ³⁶Ar₂ have been recorded between 124650cm^?1 and 127 150cm^?1 following resonant two-photon excitation via the 0⁺ _u (v¹= 0) Rydberg state located below the Ar (¹S₀) + Ar?((3p)⁵4s′ [1/2]₁) dissociation limit. Four overlapping vibrational progressions were observed and attributed to transitions to the I(1/2u) u⁺ = 35–50, I(3/2g) u⁺ = 0–10, I(1/2g) v⁺ = 0–6 and I(3/2u) v⁺ = 0–2 vibronic states of Ar⁺ ₂. The vibrational quantum numbers of the ionic states were derived from an analysis of the isotopic shifts, and the dissociation energies of the I(3/2g) (D⁺ ₀(⁴⁰Ar⁺ ₂:) = 1509.4 ± 1.2cm^?1) and the I(1/2g) (D⁺ ₀(⁴⁰Ar⁺ ₂) = 616.3 ± 1.2cm^?1) states were determined.     

Dissociation channels of silver bromide cluster Ag<Subscript>2</Subscript>Br,silver cluster Ag<Subscript>3</Subscript> and their ions studied by using alkali metal target

Various dissociation channels of silver bromide cluster ion Ag₂Br⁺ and silver cluster ion Ag₃ ⁺ were observed in high-energy collisionally-activated dissociation (CAD) using a Cs target. The fragment patterns of the high-energy CAD were compared with those of the metastable dissociation and low-energy CAD. The difference in the fragment patterns between the high-energy CAD and the other dissociation methods was explained in terms of the internal energy distributions. The dissociation mechanisms of neutral silver bromide cluster Ag₂Br and silver cluster Ag₃ were also investigated by charge inversion mass spectrometry using the Cs target. While the fragment ions AgBr^- and Ag₂ ^- were dominantly observed in the charge inversion spectrum of Ag₂Br⁺, the undissociated ion Ag₃ ^- was observed as a predominant peak in the case of Ag₃ ⁺. The dissociation behavior of Ag₂Br^* can be explained on the basis of the calculated thermochemical data. Contrary to this, the predominant existence of the undissociated Ag₃ ^- cannot be explained by the reported thermochemical data. The existence of undissociated Ag₃ ^- suggests that the dissociation barrier is higher than the internal energy of Ag₃ ^* (theoretical: 1.03 eV, experimental: 2.31 eV) estimated from the ionization potentials of Ag₃ and Cs.     

Unimolecular Decay of Metastable Cluster Anions: (O2)N−* → (O2) + O2

Unimolecular dissociation of metastable excited states of (O₂)_n^?* into (O₂) cluster anions has been detected and studied quantitatively for n in the range of 13 to 22. The apparent metastable (decay rates determined increase with cluster size in from ～ 5000 s^?1 (for n = 13) up to ～ 8500 s^?1 for n = 22).     

Measurement of the population of the4 P 5/2-state in Ar15+ by cascading processes

The population of the⁴ P _5/2-state in Ar¹⁵⁺-ions by cascading processes was measured. The corrected lifetime is (0.55±0.04) ns and is in very good agreement with the theoretical value of 0.56 ns. At a specific beam energy of 1.4 MeV/u the lifetime of the³ P ₂-state of Ar¹⁶⁺ is not influenced by cascading processes and is (1.44±0.08) ns. The energies of the³ P ₂ →¹ S ₀- and⁴ P _5/2 →² S _1/2-transitions are (3127.2±0.5) and (3090.0±0.7) eV, respectively.     

The lowest electronic states of Ne2 +, Ar2 + and Kr2 +: comparison of theory and experiment

Non-relativistic configuration interaction (CI) ab initio calculations using large basis sets have been carried out to determine the potential curves of the first electronic states of Ne₂ ⁺, Ar₂ ⁺ and Kr₂ ⁺. The spin—orbit interaction was treated assuming that the spin—orbit coupling constant is independent of the internuclear separation (R). For Ar₂ ⁺, calculated dissociation energies and equilibrium separations are in good agreement with experimental results. The calculations for Ne₂ ⁺ suggest that the lowest vibrational level of the I(1/2u) ground state observed by threshold photoelectron spectroscopy by Hall et al. [1995, J. Phys. B: At. molec. opt. Phys., 28, 2435] and assigned to either ν = 0 or ν = 2 actually corresponds to ν = 4. The calculations also predict the I(1/2g) state of Ne₂ ⁺ and Ar₂ ⁺ to possess a double-well potential and that of Kr₂ ⁺ to be repulsive at short range and to only possess a single shallow well at large internuclear separation. The ab initio calculations provide an explanation for the observation made by Yoshii et al. [2002, J. chem. Phys., 117, 1517] that Kr₂ ⁺ and Xe₂ ⁺ dissociate after photoemission from the II(1/2u) state to the I(1/2g) state whereas Ar₂ ⁺ does not.     

Effect of the dose and energy of Ar+ ions on the surface properties of vanadium and its alloys

The features of processes occurring on the surface of vanadium and its alloys irradiated using the ILU ion-beam accelerator with Ar⁺ ions at an energy of 20 and 40 keV up to doses of 5.0 × 10²¹ m^?2 and 1.0 × 10²² m^?2 at T _irr ≈ 700 K are studied. The effect of the dose and energy of implanted ions on the surface hardness is obtained. The thickness of the hardened layer is more than two orders of magnitude higher than the theoretical and experimental projected range of Ar⁺ ions at an energy of 20 and 40 keV in vanadium. Structural changes in the surface layers, which are expressed in a change in the intensity of reflections from a number of planes and an increase in the crystal-lattice parameter of the irradiated materials, are also observed.     

Experimental studies of complex crater formation under cluster implantation of solids

The results of a systematic study of surface defect formation after energetic Ar_n⁺ (n = 12, 22, 32, 54) and Xe_n⁺ (n = 4, 16) cluster ion implantation into silicon and sapphire are presented. Implantation energies vary from 3 to 18 keV/ion. Two cases of comparative studies are carried out: the same cluster species are implanted into two different substrates, i.e. Ar_n⁺ cluster ions into silicon and sapphire and two different cluster species Ar_n⁺ and Xe_n⁺ are implanted into the same kind of substrate (silicon). Atomic force, scanning electron and transmission electron microscopies (AFM, SEM and TEM) are used to study the implanted samples. The analysis reveals the formation of two types of surface erosion defects: simple and complex (with centrally positioned hillock) craters. It is found that the ratio of simple to complex crater formation as well as the hillock dimensions depend strongly on the cluster species, size and impact energy as well as on the type of substrate material. Qualitative models describing the two comparative cases of cluster implantation, the case of different cluster species and the case of different substrate materials, are proposed.     

Interaction of trapped metastable excited He atoms with solid noble gases,Ne, Ar and Kr,investigated by EPR

Local metastable excited states are found in Ne, Ar and Kr cryocrystals as He gas-discharge products are trapped in the growing cryocrystals. These states are detected by EPR and are interpreted as being local metastable excitednp⁵(n+1)s³P₂ atomic-type states in Ne, Ar and Kr cryocrystals. Analysis of the results allows the following explanation of the observed effect to be given. For the Ne cryocrystal the effect is interpreted as a new phenomenon: quasi-resonance transfer of excitation energy from the metastable He 2³S₁ atom trapped in a growing neon cryocrystal to the exciton energy band of the neon crystal followed by the exciton self-trapping into the 2p⁵3p state and subsequent decay, ending in the 2p⁵3s³P₂ state recorded by EPR in our experiment. In the case of Ar and Kr cryocrystals the effect is explained as being due to an internal ionization of the cryocrystals by the excitation energy of trapped metastable He atoms, which implies the formation in the cryocrytal of a Rg⁺ ion and a free electron in the conduction band, whereupon the fast (of 10^?12 s) self-trapping reaction of a hole follows: Rg⁺+Rg→Rg ₂ ⁺ . Thereafter the dissociative recombination reaction Rg ₂ ⁺ +e→Rg ₂ ^** →Rg+Rg*(³P₂) could take place.     

CH4或CH4+Ar介质阻挡放电中的离子能量和类金刚石膜制备

实验上，利用纯CH₄及CH₄+Ar在几百帕量级气压下的介质阻挡放电 制备类金刚石膜，研究了气压p与放电间隙d乘积(pd值)以及Ar的体积百分比R_Ar 对膜硬度的影响.理论上，从离子与气体分子的双体碰撞出发，利用较高折合电场强度E/n( 电场强度与粒子数密度之比)下离子及中性粒子速度分布的双温模型、离子在其他气体中运 动时遵守的朗之万方程及离子在混合气体中运动时遵守的布兰克法则，对CH⁺4和Ar⁺离子能量进行了分析.结果表明：1)CH₄介质阻挡 放电中，pd值由1.862×10³Pa mm降低至2.66×10²Pa mm时，CH+₄能量由5.4eV增加到163eV，类金刚石膜硬度由2.1GPa提高到17.6GPa ; 2) 保持总气压p=100Pa,放电间距d=5mm不变，在CH₄中加入Ar气，当R_Ar 由20％增加至83%时，CH⁺₄的能量由69eV增加到92eV,而Ar＋能量由93eV降低至72eV.虽然CH⁺₄能量增加有助于提高 沉积膜硬度，但当R_Ar大于67%，高强度Ar⁺轰击会导致膜表面石墨 化，膜硬度降低.为了验证离子能量理论模型的正确性，实验测量了H₂介质阻挡 放电中离子能量，测量结果与理论计算之间最大相对误差为16%. 关键词： 离子能量 介质阻挡放电 类金刚石膜     

ISS measurement of surface composition of AuCu alloys by simultaneous ion bombardments with Ar+ and He + ions

Surface composition of Au-Cu(43 at%) alloy under 1.5–5 keV argon ion bombardment has been investigated by ion scattering spectroscopy (ISS). In this experiment, we adopted a specific technique to use mixed He⁺ and Ar⁺ ions as primary beam in order to perform sputtering (Ar⁺) and ISS measurement (He⁺) simultaneously. The outermost atom layer of Au-Cu alloys under Ar⁺ ion bombardment is Au-rich leading to the conclusion that Ar⁺ ion bombardment of AuCu alloys causes the preferential sputtering of Cu atoms, resulting in a Au-rich outermost atom layer and a depletion layer of Au atoms beneath the outermost atom layer due to ion-beam-enhanced surface segregation. This result explains the experimental results obtained by AES as well.     

Unimolecular decay of hydrogen-bonded cluster ions

The unimolecular decay of the hydrogen-bonded phenol(H₂O)₄ ⁺ cluster ion was studied both experimentally and theoretically. The ion is formed by resonant two-color two-photon ionization of the neutral cluster. If the second color exceeds the dissociation threshold of the ion, fragmentation occurs on a microsecond time scale. By analyzing the time-of-flight (TOF) signal of the metastable ions at different excess energies the dependence of the fragmentation rate on the excess energy can be deduced. These experimental rates are compared to microcanonical decay constants k(E) calculated from Rice–Ramsperger–Kassel–Marcus (RRKM) theory based on ab initio data solely. Received: 8 March 2000 / Revised version: 28 April 2000 / Published online: 5 October 2000