Charge localization in collision-induced multiple ionization of van der Waals clusters with highly charged ions

Charge localization in multiple ionization and fragmentation of small argon clusters is reported. The processes are initiated by interaction of the neutral cluster with highly charged Xe(q+) (5< or =q< or =25). Products are detected by means of multicoincidence time-of-flight methods. A strong dependence of the fragmentation pattern on the Xe charge state q is observed. In particular, we find evidence for formation of multiply charged atomic Ar(r+) fragment ions up to r = 7. Such high charge states have neither been observed in fission of multiply charged van der Waals clusters nor in ion-induced fragmentation of fullerenes or metal clusters. This hints at fundamentally different excitation and fragmentation dynamics.     

Production and investigation of multiply charged metal clusters in a Penning trap

Singly charged gold cluster ions from a laser-vaporization source are transferred into a Penning trap and subjected to electron bombardment. The charged reaction products are analyzed by time-of-flight mass spectrometry after axial ejection from the trap. They include singly charged cluster fragments, multiply charged clusters of the initial size and multiply charged cluster fragments. The multiply charged clusters are selected and further investigated by collision induced dissociation. Two types of reactions can be distinguished: Dissociation into several charged fragments and evaporation of neutrals. Several features of multiply charged clusters relevant for future investigations are reviewed.This work comprises part of the dissertation of J. Ziegler.     

Highly charged clusters of fullerenes: charge mobility and appearance sizes

Clusters of fullerenes (C60,C70)(n) are produced in a gas aggregation source and are multiply ionized in collisions with highly charged Xe(20+,30+) ions. Their stabilities and decay processes are analyzed with high-resolution time-of-flight mass spectrometry. Fullerene clusters in charge states up to q=5 have been observed and appearance sizes are found to be as small as n(app)=5, 10, 21, and 33 for q=2, 3, 4, and 5, respectively. The analysis of the multicoincident fragmentation spectra indicates a high charge mobility. This is in contrast to charge localization effects which have been reported for Ar(q+)(n) rare gas clusters. Clusters of fullerenes are found to be conducting when multiply charged.     

Anomalous dielectric behavior of water in ionic newton black films

The electrostatics of two charged surfactant layers in aqueous media (surfactant/water/surfactant films) is investigated using molecular dynamics simulations. In the films studied (with a surfactant-surfactant distance from approximately 35 A to contact) we observe an anomalous dielectric response of water. The electrostatic potential phi(z) inside the aqueous core of the films (containing bulk water with rho=1 g/cm(3)) is completely different from that expected for a film containing a dielectric medium with the dielectric constant of water. In addition, our results are not consistent with a local relation between the water polarization P(z)(z) and the electric field E(z)(z). The polarization P(z)(z) is maximum at the interfaces (due to solvent molecules forming part of the structure of the surfactant layers) and decays from the interfaces inside the aqueous core with a decay length of order of approximately 10 A.     

Stability and fragmentation processes of highly charged sodium clusters

Highly charged sodium clusters produced in collisions between neutral clusters and multiply charged ions are formed within a large range of temperatures and fissilities, and identified by means of a high-resolution reflectron-type time-of-flight mass spectrometer ( m/m 14000). The limit of stability of these charged clusters is experimentally investigated, and the time-of-flight spectra are compared with theoretical spectra based on Monte-Carlo simulations. The results indicate that the maximum fissility (X) of stable clusters is approaching the Rayleigh limit (X = 1) for larger clusters sizes. It is mainly limited by the initial neutral cluster temperature ( T 100 K) and the energy transfer in the ionizing collision. In addition, the comparison between the measured and simulated spectra suggests for high cluster charges a multi-fragmentation process, in which most of charge is emitted, creating low charged residual cluster ions.     

Ellipticity-dependent of multiple ionisation methyl iodide cluster using 532 nm nanosecond laser

The dependence of multiply charged ions on laser ellipticity in methyl iodide clusters with 532 nm nanosecond laser was measured using a time-of-flight mass spectrometer. The intensities of multiply charged ions I^q+(q = 2–4) with circularly polarised laser pulse were clearly higher than those with linearly polarised laser pulse but the intensity of single charged ions I⁺ was inverse. And the dependences of ions on the optical polarisation state were investigated and a flower petal and square distribution for single charged ions (I⁺, C⁺) and multiply charged ions (I²⁺, I³⁺, I⁴⁺, C²⁺) were observed, respectively. A theoretical calculation was also proposed to simulate the distributions of ions and theoretical results fitted well with the experimental ones. It indicated that the high multiphoton ionisation probability in the initial stage would result in the disintegration of big clusters into small ones and suppress the production of multiply charged ions.     

Stability of Positively charged metallic clusters

Recent experimental results on the stability of positively charged metallic clusters are analyzed. The stability of multiply positively charged spherical Pb_n-clusters can be explained by assuming that metallic-like screening begins to occur in clusters with approximately 30 or more atoms and becomes bulk-like in clusters with approximately 300 atoms or more. Linearly shaped clusters Pb_n ⁺⁺ are stable forn6, but cease to exist for energetic reasons ifn13 atoms. Results for the stability of two-fold positively charged transition-metal clusters are also given.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

On the decay of hot metallic clusters by evaporation

Starting from the Weisskopf theory decay rates for the evaporation of cluster atoms from hot liquid alkali metal clusters are derived. The crucial input quantity is the level density which is determined from empirical properties of the bulk, namely from the specific heat and the thermal expansion coefficient. The resulting rate expression is compared with decay rate formulas given by Engelking, Klots and Gspann. Furthermore, critical (appearance) sizes of multiply charged clusters are calculated by equating the rates for neutral monomer and light charged particle emission. Also shrinking and cooling rates of large hot clusters are determined by treating multiple emission of cluster atoms, thus establishing a time scale for the decay of clusters theoretically.     

On the fragmentation of multiply charged sodium clusters

The fragmentation of multiply charged atomic sodium clusters of mass 200 is investigated using the Micro-canonical Metropolis Monte Carlo (MMMC) statistical technique for excitation energies up to 200 eV and for cluster charges up to +9e. In this work we present caloric curves and charged and uncharged fragment mass distributions for clusters with charges 0, 2, and 4. The caloric curves show a dip at the critical point implying a negative specific heat, as expected for finite systems, while the fragment mass distributions corroborate the picture of a phase transition from one dominant liquid-like cluster to complete vaporization. Received 7 November 2001 / Received in final form 4 April 2002 Published online 28 June 2002     

电离效率对激光电离团簇的高价离子产物的影响

纳秒激光与团簇相互作用产生高价离子逐渐成为分子物理界的热点之一, 为了深入研究团簇电离的本质, 本文以分子结构相似、元素组成相同的苯、环己烯和环己烷的分子团簇为对象, 利用飞行时间质谱研究了其与5 ns的532 nm激光相互作用时电离产物的价态和强度分布. 结果表明: 这三种化合物多光子电离效率苯>环己烯>环己烷, 但其高价离子的价态和比值苯是最低的, 环己烷的碳离子最高价态为4价, C³⁺和C²⁺的比值为1.1; 环己烯电离产物C³⁺和C²⁺ 的比值降低为0.6; 苯团簇的最高价态只有3价, C³⁺和C²⁺的比值约为0.4. 引起这种现象的原因可以归结于高的多光子电离效率会导致团簇多位点的电离, 引起团簇在电子加热到发生碰撞电离之前发生解离, 减小了团簇的尺寸, 进而减少了离子发生碰撞电离产生高价离子的反应时间, 最终阻碍了高价态离子的产生.     

Generation of multiply charged atomic ions of halogens using second harmonic of nanosecond Nd:YAG laser

Using the second harmonic output (532 nm) of a commercially available pulsed Nd:YAG laser interacting with pure and mixed clusters of iodo compounds, multiply charged ions of halogen group (F, Cl, Br and I) atoms have been generated based on the phenomenon of low intensity Coulomb explosion. This method provides a useful rugged tool for generation of multiply charged ions which can then be used for various applications. The effect of boiling point (vapour pressure) of the compound forming clusters has been correlated with the highest charged state of ion observed in time of flight mass spectrometer.     

Probing the largest scale structure in the universe with polarization map of galaxy clusters

We introduce a new formalism to describe the polarization signal of galaxy clusters on the whole sky. We show that a sparsely sampled, half-sky map of the cluster polarization at z approximately 1 would allow us to better characterize the very large scale density fluctuations. While the horizon length is smaller in the past, two other competing effects significantly remove the contribution of the small scale fluctuations from the quadrupole polarization pattern at z approximately 1. For the standard LambdaCDM universe with vanishing tensor mode, the quadrupole moment of the temperature anisotropy at z = 0 is expected to have an approximately 32% contribution from fluctuations on scales below 6.3 h(-1) Gpc. This percentage would be reduced to approximately 2% level for the quadrupole moment of polarization pattern at z approximately 1. A cluster polarization would shed light on the potentially anomalous features of the largest scale fluctuations.     

中等光强纳秒激光电离苯团簇产生多价碳离子的数值模拟和实验研究

飞秒强激光与团簇相互作用产生多价离子的现象已被广泛报道,然而近期多个研究小组发现当功率密度低至1010W/cm2的纳秒激光照射团簇时,同样也观察到了多价离子的存在.虽然可以用"多光子电离引发-逆韧致吸收加热-电子碰撞电离"电离机理对这种现象进行解释,但是缺乏相应的数值模拟.建立了一个简化的数值模型,根据有质动力势Up计算团簇内电子能量,再由Lotz公式计算出相应的电离截面,最后由动力学反应速率方程计算出团簇内多价碳离子随时间的演变.详细分析了团簇尺寸、电子密度等关键参数对多价离子产生的影响.数值模拟结果表明:团簇电离在小于0.7 ns时间尺度内完成,C2+,C3+和C4+多价离子强度达到平衡后,离子相对强度由大到小依次为C2+,C3+,C4+,这与实验结果相一致;多价离子的价态随着团簇尺寸的增加而升高,半径为5.6 nm的苯团簇比半径为3 nm的苯团簇更容易产生高价态的离子,这也与实验结果相一致.     

Cluster-assisted generation of multicharged ions in nanosecond laser ionization of carbon bisulfide clusters at 1064nm

The photoionization of seeded carbon bisulfide molecular beam by a 1064\,nm nanosecond Nd-YAG laser with intensities varying from $0.8\times10^{11}$ to $5.6\times10^{11}$\,W/cm$^{2}$ have been studied by time-of-flight mass spectrometry. Multiply charged ions of S$^{q + }$ ($q$ = 2--6) and C$^{q +}$ ($q$ = 2--4) with kinetic energy of hundreds of electron volts have been observed, and there are strong experimental evidences indicating that those multicharged ions originate from the ionization of CS$_{2}$ neat clusters in the beam. An electron recolliding ionization model is proposed to explain the appearance of those multiply charged atomic ions under such low laser intensities.     

Recombination processes in atomic clusters irradiated by superintense femtosecond laser pulses

Various mechanisms of recombination of electrons with multiply charged atomic ions in atomic clusters irradiated by superintense femtosecond laser pulses are discussed. All of the recombination mechanisms are shown to take a time considerably longer than the laser pulse duration and, hence, they can develop only in a homogeneous, fairly rarefied cluster plasma after pulse termination. All autoionization states of multiply charged ions in a dense cluster plasma have been found to be destroyed by the Holtsmark electric field.     

CO2在中性及带负电Be（n=4, 7, 10, 12, m=0, -1）团簇表面的吸附与解离

运用密度泛函理论,对中性及带负电的BeCO2 (n=4, 7, 10, 12, m=0, -1) 团簇进行了构型优化,稳定性和电子性质分析。结果表明：CO2吸附于Ben和Ben-1团簇表面时,C-O键长均有不同程度的伸长。其中Be4CO2-1,Be12CO2-1中CO2分子的一个C-O键自然断裂(伸长量达到了134%和156%),为典型的解离性吸附。Be团簇表现出了较好的吸附CO2分子的能力,特别是带负电以后,吸附能明显增大(约为3.16eV--5.965eV)。电子性质分析表明,带负电升高了相应团簇的前线轨道能级,使轨道杂化发生在费米能级处附近,从而增强了CO2分子与相应团簇的成键能力。     

Structural and electronic properties of neutral clusters Ga12X (X=C, Si, Ge, Sn, and Pb) and their anions from first principles

The structural and electronic properties of neutral and negatively charged Ga₁₂X (X=C, Si, Ge, Sn, and Pb) clusters are calculated by the first-principles method. The results show that the most stable symmetry depends on the doped atom rather than the geometry structure. However, the geometry symmetry plays an important role in calculating the energy gap. In addition, in the anionic clusters, the added electron would reduce the energy gap by about 0.4 eV. As for the density of states (DOS), clusters with the same symmetry show a similar trend of DOS. The major impact on DOS by adding an electron is the occurrence of relative energy shift.     

Nuclear fragmentation degree in the production of light projectile fragments

The projectile-target multiplicity correlations at the lowest (3.7 A GeV) and highest (200 A GeV) available energies in Sulfur-emulsion interactions are investigated in the framework of the participant-spectator model. We examined the light projectile spectator (singly, N_z=1 and doubly, N_z=2 charged projectile fragments). The measured average multiplicities of N_z=1 and N_z=2 at both incident energies showed a decrease with increasing the fragment charge, as well as the average values within experimental errors showed independence on the incident energy. The multiplicity measurements of different emitted secondary charged particles (produced particles, shower tracks, and target fragments, gray and black tracks) in the interactions of ³²S-Em at 3.7 A and 200 A GeV were carried out. However, the correlation between the mean multiplicities of secondary charged particles and both of the singly and doubly charged projectile fragments were investigated to shed some light on the interface of spectator and participant regions, and on the possible influences of the phenomena from the two regions on the collision dynamics.     

Dynamic scaling approach to glass formation

Experimental data for the temperature dependence of relaxation times are used to argue that the dynamic scaling form, with relaxation time diverging at the critical temperature T(c) as (T-T(c))(-nuz), is superior to the classical Vogel form. This observation leads us to propose that glass formation can be described by a simple mean-field limit of a phase transition. The order parameter is the fraction of all space that has sufficient free volume to allow substantial motion, and grows logarithmically above T(c). Diffusion of this free volume creates random walk clusters that have cooperatively rearranged. We show that the distribution of cooperatively moving clusters must have a Fisher exponent tau=2. Dynamic scaling predicts a power law for the relaxation modulus G(t) approximately t(-2/z), where z is the dynamic critical exponent relating the relaxation time of a cluster to its size. Andrade creep, universally observed for all glass-forming materials, suggests z=6. Experimental data on the temperature dependence of viscosity and relaxation time of glass-forming liquids suggest that the exponent nu describing the correlation length divergence in this simple scaling picture is not always universal. Polymers appear to universally have nuz=9 (making nu=3 / 2). However, other glass-formers have unphysically large values of nuz, suggesting that the availability of free volume is a necessary, but not sufficient, condition for motion in these liquids. Such considerations lead us to assert that nuz=9 is in fact universal for all glass- forming liquids, but an energetic barrier to motion must also be overcome for strong glasses.     

How multivalency controls ionic criticality

To understand how multivalency affects criticality in z:1 ionic fluids, we report an ion-cluster association theory embodying ionic solvation and excluded volume for equisized hard-sphere models with z=1-3. In accord with simulation but contradicting integral equation and field theories, the reduced critical temperature falls when z increases while the density rho(c) rises steeply. These trends can be explained semiquantitatively by noting that 80%-90% of the ions near T(c) are bound in neutral or charged clusters, depleting the ionic strength. For z not equal 1, predicted interphase Galvani potentials vanish at T(c).