Neutral and ionic clusters of antimony and bismuth: A comparison of magic numbers
TL;DR: In this paper, neutral and singly charged anion or cation clusters of antimony and bismuth are produced by laser vaporization in a pulsed nozzle cluster source.
Abstract: Neutral and singly charged anion or cation clusters of antimony and bismuth are produced by laser vaporization in a pulsed nozzle cluster source. Neutral clusters are photoionized near threshold with a fluorine excimer laser, while ionized clusters are sampled directly from the laser vaporization plasma. All species are mass analyzed with a time‐of‐flight spectrometer. Abundance patterns in these systems exhibit ‘‘magic numbers’’ that are strikingly charge dependent. Compared at the same charge, corresponding neutral and cation spectra of these metals are quite similar, but significant differences arise in the two anion cluster distributions. Neutral cluster growth in these systems ends abruptly at five atoms while the ionized distributions fall off gradually out to beyond 12–15 atoms. These unique patterns are examined in the context of cluster growth dynamics and suspected cluster stability based on the predictions of simple electron counting models.
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TL;DR: Reactions of O2(∆g) are associated with significant applications in several fields, including organic synthesis, bleaching processes, and, most importantly, the photodynamic therapy of cancer, which has now obtained regulatory approval in most countries for the treatment of several types of tumors.
Abstract: For more than 70 years, researchers in several areas of science have been intrigued by the physical and chemical properties of the lowest excited states of molecular oxygen. With two singlet states lying close above its triplet ground state, the O2 molecule possesses a very unique configuration, which gives rise to a very rich and easily accessible chemistry, and also to a number of important photophysical interactions. In particular, photosensitized reactions of the first excited state, O2(∆g), play a key role in many natural photochemical and photobiological processes, such as photodegradation and aging processes including even photocarcinogenesis. Reactions of O2(∆g) are associated with significant applications in several fields, including organic synthesis, bleaching processes, and, most importantly, the photodynamic therapy of cancer, which has now obtained regulatory approval in most countries for the treatment of several types of tumors. The development of both applications and novel observation techniques has strongly accelerated during the past few years. Significant recent advances include, for example, the development of novel luminescent singlet oxygen probes,1-4 the time-resolved detection of O2(∆g) in a transmission microscope,5 the first time-resolved measurements of singlet oxygen luminescence in vivo,6 and the observation of oxygen quenching of triplet-excited single molecules.7 Experimental and theoretical studies on the mechanisms of photosensitized formation of excited O2 states and of their deactivation have been performed for almost 40 years. While most early liquid-phase studies were exclusively concerned with O2(∆g), recent technological advances also made possible time-resolved investigations of the second excited state, O2(Σg), which can be formed in competition with O2(∆g) in many cases. A significant number of * Corresponding author. Tel.: ++49 69 79829448. Fax: ++49 69 79829445. E-mail: R.Schmidt@chemie.uni-frankfurt.de. 1685 Chem. Rev. 2003, 103, 1685−1757
1,721 citations
TL;DR: In this paper, a reaction between a metal atom and silicon in a supersonic jet to form metal atom-silicon clusters was observed, and the dominant product peaks observed in the mass spectra obtained for all three group VIB metals correspond to identical but remarkable cluster stoichiometries.
Abstract: We report observation of a reaction between a metal atom and silicon in a supersonic jet to form metal atom–silicon clusters. Using the technique of laser vaporization supersonic expansion with metal carbonyl seeded carrier gas, clusters of the form MSin have been detected by ArF and F2 laser photoionization time‐of‐flight mass spectrometry. Three group‐VIB transition metals and copper have been investigated. The dominant product cluster peaks observed in the mass spectra obtained for all three group VIB metals corresponds to identical but remarkable cluster stoichiometries. The dominant product peaks have formulas given by MSin where n=16. Copper results are different than the other three metals, indicating the importance of the metal valence electronic structure to the chemistry. The metal–semiconductor clusters are relatively more stable towards photofragmentation than the bare silicon cluster of the same size. The observation of these new species may be relevant to reactions which occur at the interfa...
227 citations
TL;DR: All aspects of the design of the laser vaporization cluster source are examined, discussing the relevant chemistry, physics, and mechanical aspects of experimental configurations employed by different labs.
Abstract: The laser vaporization cluster source has been used for the production of gas phase atomic clusters and metal-molecular complexes for 30 years. Numerous experiments in the chemistry and physics of clusters have employed this source. Its operation is simple in principle, but there are many subtle design features that influence the number and size of clusters produced, as well as their composition, charge state, and temperature. This article examines all aspects of the design of these cluster sources, discussing the relevant chemistry, physics, and mechanical aspects of experimental configurations employed by different labs. The principles detailed here provide a framework for the design and implementation of this source for new applications.
205 citations
TL;DR: It is proposed that the complex behaviour of GaSb originates from a combination of spatially correlated evaporation events and the subsequent field induced dissociation of cluster ions, the latter contributing to inaccuracies in the overall atom probe composition determination for this material.
101 citations
TL;DR: In this article, the electronic structure and chemical bonding of the pentapnictogen cluster anions, Pn5- (Pn = P, As, Sb, and Bi), were investigated using both photoelectron spectroscopy and ab initio calculations.
Abstract: The electronic structure and chemical bonding of the pentapnictogen cluster anions, Pn5- (Pn = P, As, Sb, and Bi), were investigated using both photoelectron spectroscopy and ab initio calculations. Well-resolved photoelectron spectra were obtained for the anions at several photon energies and were analyzed according to the theoretical calculations. The ground state of all the Pn5- species was found to be the aromatic cyclic D5h structure with a C2v low-lying isomer. We found that the C2v isomer gains stability from P5- to Sb5-, consistent with the experimental observation of the coexistence of both isomers in the spectra of Sb5-. The valence molecular orbitals (MOs) of the D5h Pn5- were analyzed and compared to those of the aromatic C5H5- hydrocarbon. The same set of π-MOs is shown to be occupied in the D5h Pn5- and C5H5- species, except that the MO ordering is slightly different. Whereas the three π-MOs in C5H5- all lie above the σ-MOs, the third π orbital (1a2‘ ‘ in Pn5-) lies below the σ-MOs. The stab...
90 citations
References
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TL;DR: In this paper, a mass spectra for sodium clusters of $N$ atoms per cluster, produced in a supersonic expansion with argon carrier gas, is presented. The spectra show large peaks or steps at $N=8, 20, 40, 58, \mathrm{and} 92$.
Abstract: Mass spectra are presented for sodium clusters of $N$ atoms per cluster ($N=4\ensuremath{-}100$) produced in a supersonic expansion with argon carrier gas. The spectra show large peaks or steps at $N=8, 20, 40, 58, \mathrm{and} 92$. These can be understood in terms of a one-electron shell model in which independent delocalized atomic $3s$ electrons are bound in a spherically symmetric potential well.
1,909 citations
TL;DR: In this paper, the borane-carborane structural pattern has been studied in a wide range of other compounds, including metal clusters, metal-hydrocarbon 7∼ complexes, and various neutral or charged hydrocarbons.
Abstract: Publisher Summary This is one of two articles in this volume that is concerned with the borane-carborane structural pattern. In the other, Williams has shown how the pattern reflects the coordination number preferences of the various atoms involved. The purpose of the present article is to note some bonding implications of the pattern, and to show its relevance to a wide range of other compounds, including metal clusters, metal-hydrocarbon 7∼ complexes, and various neutral or charged hydrocarbons. Boranes and carboranes may be regarded as cluster compounds in the sense defined by Cotton; they contain a finite group or skeleton of atoms held together entirely, mainly, or at least to a significant extent by bonding directly between those atoms, even though some other atoms may be associated intimately with the cluster. Examples of their structural pattern, however, can be found far beyond the confines of what is normally regarded as cluster chemistry, so this survey includes many systems not commonly referred to as clusters.
1,235 citations
TL;DR: In this paper, the approach to the bulk of a transition-metal cluster is described, with a focus on the development of band structure and the response of clusters to external magnetic moments and electric polarizabilities.
Abstract: Functions of Size: The Approach to the Bulk A. Ionization Potentials, Electron Affinities, and the Development of Band Structure B. Response of Clusters to External Fields: Magnetic Moments and Electric Polarizabilities C. Metal Cluster Structure and Interatomic Distances 0. Dissociation of Multiply Charged Clusters: Coulomb Explosions E. Chemical Reactions of Neutral Clusters F. Chemical Reactions of Ionized Clusters 111. Properties of Transition-Metal Clusters as
1,210 citations
TL;DR: In this article, a survey study of the reactivity of transition metal clusters in contact with low concentrations of D2, N2 and CO is presented. But the detailed pattern of reactivity differing markedly for each metal.
Abstract: Reactions on the surface of a variety of transition metal clusters have been studied in the gas phase at near room temperature using a newly developed fast-flow reaction device. Initial examples of the use of this device are provided by survey studies of the reactivity of iron, cobalt, nickel, copper, and niobium clusters in contact with low concentrations of D2, N2 and CO. Dissociative chemisorption of D2 is found to occur with dramatic sensitivity to cluster size in the cases of iron, cobalt, and niobium clusters, the detailed pattern of reactivity differing markedly for each metal. The corresponding reaction is also observed with nickel clusters, but here the reactivity shows only a slow, steady increase with cluster size. Copper clusters are found to be completely unreactive to H2 chemisorption under these conditions. Molecular nitrogen is found to chemisorb readily to clusters of cobalt and niobium, with a reactivity pattern very similar to that observed with D2. Iron clusters are found to show slight reactivity with N2; only a small amount of chemisorption is observed on the most reactive clusters at high N2 concentration, but the pattern of this reactivity with cluster size is consistent with that observed in D2 chemisorption. In contrast to these highly structured reactivity patterns of D2 and N2, carbon monoxide is found to show only a slow, monotonic increase in reactivity with cluster size. It is suggested that these dramatic reactivity patterns for chemisorption on metal clusters provide stringent tests for future theories as to the nature of chemisorption on metal surfaces at a detailed, molecular level.
344 citations
TL;DR: In this article, photoelectron spectra of the copper cluster anions yield measurements for vertical electron binding energies and adiabatic electron affinities as a function of cluster size.
Abstract: Negative ion photoelectron spectra of Cu−n (n=1–10) are reported for the 0–2.4 eV region at an instrumental resolution of 10 meV. The cluster anions were prepared in a flowing afterglow ion source incorporating a cold cathode dc discharge. This very simple source provides a convenient, general method to prepare continuous beams of near‐thermal metal cluster ions at intensities (up to 10−11 A) sufficient for spectroscopic or chemical studies. Photoelectron spectra of the copper cluster anions yield measurements for vertical electron binding energies and adiabatic electron affinities as a function of cluster size. The overall trend observed is well described by the classical spherical drop electrostatic model. In addition, quantum effects are apparent in the higher electron affinities generally observed for clusters containing odd numbers of atoms. Excited electronic states in the photoelectron spectra show that the transition energy in the neutral molecule decreases rapidly with cluster size. Vibrational structure resolved in the Cu−2 spectrum yields measurements for the vibrational frequency (210±15 cm−1), bond length (2.345±0.010 A), dissociation energy (1.57±0.06 eV), and vibrational temperature (450±50 K) of the anion.
306 citations