Fluorescence of rare gas clusters excited with synchrotron radiation

A cluster beam experiment for fluorescence measurements on rare gas clusters has been built up. First results on the evolution of energy levels of neutral krypton clusters with a cluster size between 200–8500 atoms/cluster are reported. The well known bulk excitons of solid krypton do not merge into the first atomic lines and appear only in clusters larger than 300 atoms/cluster. Smaller clusters absorb only at energies which fit well with surface excitons of the solid.     

Adsorption of polar molecules on krypton clusters

The formation process of binary clusters has been studied using synchrotron based core level photoelectron spectroscopy. Free neutral krypton clusters have been produced by adiabatic expansion and doped with chloromethane molecules using the pickup technique. The comparison between the integrated intensities, linewidths, and level shifts of the cluster features of pure krypton and of chloromethane-krypton clusters has been used to obtain information about the cluster geometry. We have shown that most of the chloromethane molecules remain on the surface of the clusters.     

TPEPICO studies near ionization threshold of argon and krypton clusters

Single photon ionization of argon and krypton clusters has been studied in the region between threshold and the ionization potential of the corresponding atom. Synchrotron radiation from the electron storage ring BESSY is used to ionize the clusters; threshold-photo-electron-photoion-coincidence (TPEPICO)-time-of-flight technique is used to detect ions correlated with the emission of zero-kinetic-energy-electrons. The spectra of the clusters in the range ofn=2 to 15 are discussed in view of the extensive fragmentation taking place in these systems. In order to characterize the properties of the clusters a method using scaling laws is applied. The principles and the deduction of Hagena's scaling parameter Γ* are briefly reviewed. Using Γ* an experimentally derived mean cluster size for molecular beams can be assigned. This allows one to clearly demonstrate the systematic variations of the measured spectra due to cluster fragmentation. As a general feature it is observed that, in the range studied, the peak in the measured ionization rate for a cluster ion (fragment) of a given size shifts to higher photon energies as the mean cluster size is increased.     

Electron-ion-coincidence spectra of K-shell excited Ne, Ar, and Kr clusters

Electron-ion-coincidence spectra were recorded for K-shell excited krypton, argon, and neon clusters covering the size range from 1 atom to about 3000 atoms by utilizing hard x-ray undulator beamlines. Multiply charged ions Rz+(z>or=2) and singly charged ions Rn+(n>or=1) are observed as cluster fragments, and their relative abundance exhibits a characteristic dependence on the average cluster size N. It is expected from these results that the charges generated on the cluster surface are strongly localized while those in the cluster core are more delocalized. The estimated charge separation distance increases with N, and it is longer for lighter elements.     

Cluster size effects in vuv radiation spectra of argon and krypton supersonic jets

The relation between VUV radiation spectra of argon and krypton supersonic jets excited by an electron beam and the mean size of clusters in a jet is studied. For each atomic and molecular emission of argon in the 104–120 nm range and of krypton from 116 to 130 nm, the maximum intensity is found to occur when electrons collide with clusters of a definite mean size. It is found that self-localized excitons of atomic type or diatomic excimer molecular type with a small binding energy (several hundredths of an eV) are mainly formed in outer icosahedral shells of argon or krypton clusters and those of diatomic excimer molecular type with a large binding energy (several tenths of an eV) arise principally in inner shells.     

Infrared spectra of water clusters in krypton and xenon matrices

The infrared absorption spectra of the water molecules and small water clusters, (H(2)O)(n) with n = 2-6, trapped in solid argon, krypton, and xenon matrices have been investigated. The infrared bands of the water clusters with n = 5 and 6 in krypton and n = 3, 4, 5, and 6 in xenon matrices have been identified for the first time in the bonded OH stretching region. The frequency shifts in the bonded OH stretching band of the water dimer and trimer in xenon matrices show fairly large deviations to the red from the empirical correlation between the matrix shifts and the square root of the critical temperatures of the matrix material. The observed anomalous shifts suggest that the water dimer and trimer in solid xenon are trapped in multiple sites, and that the structures of the preferential trapping sites are different from those in argon and krypton matrices.     

Photoionization of small krypton clusters in the Kr 3d regime: evidence for site-specific photoemission

Kr 3d ionization energies of small, variable size krypton clusters are investigated by photoelectron spectroscopy, where the size regime of clusters with an average size N< or =30 is studied. Characteristic shifts in Kr 3d ionization energies to lower binding energies are found compared to the bare atom. These are also different from those of large krypton clusters. Moreover, we find evidence for photoionization of the krypton dimer. Its 3d ionization energy is barely shifted relative to the atomic value. Results from model calculations considering different isomers and cluster sizes as well as defect sites give evidence that the experimental results can be related to photoionization from different surface sites in variable size krypton clusters. This can be related to site-specific photoemission in small Kr clusters. The results are compared to size effects in Kr 3d near-edge features of variable size Kr clusters as well as recent results on Kr 3d photoionization of large Kr clusters.     

Ejection of cluster ions as a result of electron impact ionization of argon clusters

Time evolution of mass distribution of argon cluster ions has been studied in pulsed jets (pulse duration≈0.4 ms) by retarding potential method. The ejection of cluster ions of the order of 180 atoms from cluster ions of the order of 500 atoms has been revealed. The ejection has a threshold character as a function of the time elapsed after electron impact ionization. The threshold time was about 20 μs. Delayed non-thermal fragmentation of the cluster ions testifies that the self-trapped ion, formed in argon clusters as a result of ionization, can live for a long time in its excited state without dissipation of the excess energy to the cluster. This ion should be located on the surface of the cluster. Energetic analysis of the fragmentation is consistent with the size of the ejected clusters. A model of the observed time evolution of the delayed fragmentation is herein proposed.     

Production of large sodium clusters (Nax,.x⩽65) by seeded beam expansions

Seeded beam expansions of high-temperature sodium vapour in helium, neon, argon, krypton and nitrogen carrier gases are examined. Photoionization coupled with mass spectroscopic detection is used to determine beam constituents. Contrary to non-seeded supersonic expansions, in which the abundance of sodium clusters observed decreases exponentially with increasing cluster size, large abundances of higher clusters (Na_x, x ?65) are observed. Maxima centered at m/z = 161, m/z = 437 and m/z = 874 occur under certain conditions.     

覆盖的氩原子簇过热的分子动力学模拟(英)

通过分子动力学模拟研究了覆盖较高熔点的原子的氩原子簇．原子族由177个氩原子和72个覆盖原子组成．覆盖原子的势能参数ε比氩原子大50％，该原子簇比纯氩原子簇熔点过热2K．模拟结果表明，覆盖的原子簇过热的原因是：在达到熔点之前，体系缺少氩原子构成的自由表面，仍然是覆盖原子的有序表面．     

Magic numbers of large rare gas clusters

The superior stability of closed-shell icosahedral structures is evident from size distributions of argon, krypton and xenon cluster ions in the size range 100?n?1000.     

ChemInform Abstract: Investigation of Praseodymium Fluorides: A Combined Matrix‐Isolation and Quantum‐Chemical Study.

Reaction products of laser‐ablated praseodymium atoms with fluorine in excess neon, argon, krypton, or neat fluorine at 4—10 K are investigated by IR spectroscopy and quantum chemical DFT and coupled‐cluster calculations.     

Argon cluster-ion sputter yield: Molecular dynamics simulations on silicon and equation for estimating total sputter yield

Argon Gas Cluster-Ion Beam sources have become widely-used on X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) instruments in recent years, but there is little reference data on sputter yields in the literature as yet. Total sputter yield reference data is needed in order to calibrate the depth scale, of XPS or SIMS depth profiles. We previously published a semi-empirical ‘Threshold’ equation for estimating cluster total sputter yield from the energy-per-atom of the cluster and the effective monatomic sputter threshold of the material. This has been shown to agree extremely well with sputter yield measurements on a range or organic and inorganic materials for clusters of around a thousand atoms. Here we use the molecular dynamics (MD) approach to explore a wider range of energy and cluster size than is easy to do experimentally to high precision. We performed MD simulations using the ‘Large-scale Atomic/Molecular Massively Parallel Simulator’ (LAMMPS) parallel MD code on high-performance computer (HPC) systems. We performed 1150 simulations of individual collisions with a silicon (100) surface as an archetypal inorganic substrate, for cluster sizes between 30 and 3000 argon atoms and energies in the range 5 to 40 eV per atom. This corresponds to the most important regime for experimental cluster depth-profiling in SIMS and XPS. Our MD results show a dependence on cluster size as well as energy-per-atom. Using the exponent previously suggested by Paruch et al., we modified the Threshold model equation published previously to take this into account. The modified Threshold equation fits all our MD results extremely well, building on its success in fitting experimental sputter yield measurements. This work is submitted to the volume dedicated to Dr. Martin P Seah, MBE, who was a great influence on the early career of one of the authors (PJC) and who himself made many valuable contributions to the literature on sputtering as it relates to surface and interface analysis.     

硅酸盐岩石微孔中流体混合物扩散系数的分子动力学模拟

用计算机模拟研究了受限于硅酸盐岩石微孔中等摩尔氩氪流体混合物的扩散系数.为验证程序的正确性,分别将宏量条件下氩和氪的分子动力学模拟值与文献实验值进行了比较.然后,对受限于硅酸岩平板壁面中氩氪流体混合物的扩散系数进行了模拟计算.根据计算结果提出了五个不同对比壁间距下氩氪混合流体扩散系数的经验模型,这些模型可应用于工业估算.     

Frequency-dependent hyperpolarizabilities of the Ne, Ar, and Kr atoms using the approximate coupled cluster triples model CC3

The frequency-dependent electric field-induced second harmonic generation (ESHG) second hyperpolarizabilities gamma of neon, argon, and krypton are calculated using the approximate coupled cluster triples model CC3. Systematic basis set investigations are carried out to establish basis set limits, and scalar relativistic effects are accounted for by direct perturbation theory. To estimate higher-order correlation effects, full configuration-interaction results are used to benchmark the accuracy of CC3. The best theoretical estimates obtained thereby for the static second hyperpolarizabilities gamma(0) are 107.4, 1159, and 2589 a.u. for neon, argon, and krypton, respectively. These values as well as the results for the dispersion curve of the parallel component gamma( parallel) agree well with the latest experimental values from electric field-induced second harmonic generation. In addition, the dispersion of the perpendicular component gamma( perpendicular) and the hyperpolarizability ratios gamma( parallel)gamma( perpendicular) has been studied for the first time on a consistently correlated ab initio level. The analysis of the results indicates that, in particular for neon and krypton, the presently available experimental values are flawed.     

Electronic spectroscopy of toluene-rare-gas clusters: the external heavy atom effect and vibrational predissociation

Toluene-X van der Waals clusters (where X = Ne, Ne2, Ar, Ar2, Kr, Xe) have been investigated by fluorescence excitation spectroscopy in the region of the S1-S0 transition. With the exception of Xe, for each rare-gas studied, we have assigned cluster transitions in the region of all the strong monomer vibrational bands up to 1000 cm(-1) above the origin band. We have further investigated the S1 relaxation dynamics for each vibrational level of each complex, via their fluorescence decay profiles. Clustering with neon has little appreciable effect on the vibrationless S1 lifetime. By contrast, the clusters with argon and krypton exhibit markedly shorter fluorescence lifetimes compared with the monomer. The effect is so severe in the case of toluene-Xe clusters that no fluorescence signals were observed. We interpret these results in terms of an external heavy atom effect in which the rate of intersystem crossing in toluene is influenced by the cluster partner. For clusters built upon excited S1 vibrational levels, the situation is potentially complicated by intramolecular vibrational redistribution and vibrational predissociation (VP). The majority of the fluorescence decay profiles were satisfactorily modeled using single exponential decays. The emission following pumping of the 37(1) level in the toluene-Kr cluster, however, is an exception. We have modeled the decay of this level with a simple kinetic scheme including VP and determined a predissociation rate of (1.04 +/- 0.54) x 10(7) s(-1).     

Emission characteristics of nickel ionic lines excited by reduced-pressure laser-induced plasmas using argon, krypton, nitrogen, and air as the plasma gas

The emission characteristics of nickel ionic lines in low-pressure laser-induced plasmas are investigated when argon, krypton, nitrogen, or air gas was employed as the plasma gas. The spectrum patterns and the relative intensities of the ionic lines are measured with and without a blind cylinder surrounding the sample surface to separate the detected emission area into two portions roughly: an initial breakdown zone and an expansion zone of the plasma. Their emission intensities are strongly dependent on both the kind and the pressure of the plasma gas. Different major ionic lines are observed in the argon and the krypton plasmas: for example, the Ni II 230.010-nm line (8.25 eV) for argon and the Ni II 231.604-nm line (6.39 eV) for krypton. The excitation mechanism of these ionic lines is considered to be a resonance charge-transfer collision with argon or krypton ion due to good energy matching to the corresponding energy levels of nickel ion. These ionic lines measured with the blind cylinder at reduced pressures of around 1300 Pa give the largest signal-to-background ratios; therefore, the analytical application under such optimum plasma conditions is recommended.     

Possible electronic decay channels in the ionization spectra of small clusters composed of Ar and Kr: a four-component relativistic treatment

In this work single and double ionization spectra of the homo- and heteronuclear argon/krypton dimers and trimers are calculated by means of propagator methods where a four-component implementation was employed for the single ionizations. Scalar relativistic effects play only a minor role for the outer valence spectral structure, whereas spin-orbit coupling and electron correlation have to be treated adequately in order to reproduce the features correctly. Nonradiative decay mechanisms of subvalence vacancies in the argon and krypton dimers and trimers are discussed both for the interatomic Coulombic decay and the electron transfer mediated decay (ETMD). In the heteronuclear triatomic system which serves as a model for larger clusters, a possible ETMD process of the Ar 3s vacancy is found for the linear arrangement of the atoms. In the bent configuration the ETMD channel is closed.     

Molecular dynamics simulation of copper removal from graphene by Bombardment with argon clusters

The problem of developing a nondestructive method for purification of graphene to remove a deposited metal has been tackled. Bombardment of copper film-precoated graphene by argon clusters has been simulated in terms of molecular dynamics. With a flow of 30-eV clusters directed parallel to the graphene sheet plane, the full removal of copper from graphene is achieved. The mobility of Cu and C atoms, the distribution of a stress that is the most susceptible to cluster impact in the graphene plane, and the graphene sheet surface roughness during the simulated process have been determined.     

Rydberg states of small NaAr(n)* clusters

The 4s and 5s Rydberg excited states of NaAr(n)* clusters are investigated using a pseudopotential quantum-classical method. While NaAr(n) clusters in their ground state are known to be weakly bound van der Waals complexes with Na lying at the surface of the argon cluster, isomers in 4s or 5s electronically excited states of small NaAr(n)* clusters (n< or =10) are found to be stable versus dissociation. The relationship between electronic excitation and cluster geometry is analyzed as a function of cluster size. For both 4s and 5s states, the stable exciplex isomers essentially appear as sodium-centered structures with similar topologies, converging towards those of the related NaAr(n)+ positive ions when the excitation level is increased. This is consistent with a Rydberg-type picture for the electronically excited cluster, described by a central sodium ion solvated by an argon shell, and an outer diffuse electron orbiting around this NaAr(n)+ cluster core.