Effects of solvation on dissociative electron attachment to methyl iodide clusters

Using laser photoelectron attachment to methyl iodide clusters in a differentially-pumped seeded supersonic helium beam and mass spectrometric ion detection, we have measured the rate coefficients for formation of (q = 0-2) ions over the electron energy range 0-100 meV with an effective energy width of about 2.5 meV. Whereas a prominent vibrational Feshbach resonance just below the onset for the C-I stretch vibration ( ) is observed for dissociative attachment to monomers (yielding I^- ions), only weak and broad structure, shifted to lower energies, is detected for formation of ions and essentially no structure is left in the attachment spectrum for . These observations are interpreted by model R-matrix calculations which successfully describe the DA cross-section for the monomer and qualitatively recover the trend observed for cluster ion formation. For the clusters, the effects of increased electron-target long-range interaction and of solvation as well as coupling to soft vibrational modes lead to strong broadening and shifting of the vibrational Feshbach resonance and, ultimately, to its disappearance. Received 29 November 1999 and Received in final form 14 January 2000     

Systematic study of small BN clusters

We performed a systematic investigation of the small B_xN_y (x + y? 6) clusters using the ab initio Hartree-Fock scheme plus second-order perturbation theory. The nature of the potential energy surface extrema are analyzed through analytical total energy second derivatives. Ionization potentials, binding energies and the stability against some possible reaction mechanisms are calculated. Based on these results we propose that the growing process for these clusters is mainly due to the successive incorporation of BN molecules. A discussion of some mass spectrometry experimental results is also presented. Received 2 October 2000     

An inelastic threshold in electron - alkali cluster collisions

An analysis of integral cross sections for slow electron collisions with neutral sodium clusters and nanoparticles reveals that, in addition to an effective negative ion formation channel, there exists a strong inelastic threshold-type process which appears above a collision energy of 1-1.3 eV. We show that it can be plausibly associated with the onset of direct electron-induced cluster fragmentation. This result highlights the importance of understanding the dynamics of electron-vibrational energy transfer in nanoclusters, including the relative probability of direct vs. statistical energy transfer. Received 24 November 2000     

Low-energy surface collision induced dissociation of Ge and Sn cluster ions

Fragmentation of germanium and tin cluster ions in the low-energy collisions with a Si surface has been investigated by means of a tandem time-of-flight mass spectrometer. At low incident energies, smaller clusters fragmented by an atom loss process, whereas larger clusters decayed by fission. The favored fragmentation paths for both cluster ions were similar to those for Si cluster ions. The results support the structural similarities among Si, Ge, and Sn clusters in the present size range. For tin cluster ions, low-energy fragmentation patterns were compared with those obtained from theoretical calculations using generalized gradient approximation (GGA) and the B3PW91 exchange-correlation functional. It has been found that the B3PW91 hybrid functional results are consistent with the experimental observations.     

Electron detachment and fragmentation in collisions between 1.25 keV/carbon and clusters and

The destruction cross-section for 22.5 and 50 keV C^1- , for 10 and 50 keV C₈ ^1- and for 50 and 75 keV C₆₀ ^1- clusters in collisions with H₂ has been measured by an attenuation method. The destruction of the cluster anions is dominated by electron detachment rather than fragmentation and is of the order of the geometric cross-section. The cross-sections vary little with bombarding energy. Received: 16 September 1998 / Received in final form: 23 February 1999     

Changing the fragmentation pattern of molecules in helium nanodroplets by co-embedding with water

Individual amino acid molecules embedded in helium nanodroplets fragment extensively when the beam is ionized by electron bombardment. However, we find that when glycine and tryptophan are picked up right after, or right before, a small amount of water, the mass spectra become significantly altered. For glycine, the detected ions consist almost entirely of intact protonated amino acids, with or without a few water molecules attached. In other words, the presence of water exerts a striking “buffering” effect on the ionization-induced fragmentation. For tryptophan the effect is weaker but also present. In both cases, the hydroxyl group lost upon ionization overwhelmingly comes from the water partner (in strong contrast to the situation observed when amino acids are picked up by neat water clusters). A complementary experiment involving DCl molecules co-embedded with water shows that in this case Cl and/or DCl invariably leave the droplet upon ionization. The observed patterns may be steered by the analytes' dipole moments or by solvation effects.     

Nanostructuring of single crystal diamond by reactive and non-reactive accelerated cluster erosion

Reactive accelerated cluster erosion (RACE) of single crystal artificial diamond has been used to fabricate various nano- and microstructures. Carbondioxide clusters of about 1000 molecules are accelerated to 100 keV to act as the eroding agent. Using movable shadow masks, the accelerated cluster beam may erode staircase structures acting as an optical grating. A cycloid gear has been generated via a stationary nickel mask. Non-reactive accelerated cluster erosion using argon clusters will be considered for comparison. Received 30 November 2000     

EICO measurements of inner-core excited mixed rare-gas clusters

The spectra of deep inner-core excited mixed rare-gas clusters were recorded by using electron ion coincidence (EICO) and multi-hit momentum imaging (MHMI) techniques. The EICO spectra for Ar₉₉Kr₁ clusters reveal that singly charged ions are emitted from the inner-core excited clusters in addition to the multiple charged ions. The dependence of the EICO spectra on photon energy and cluster size suggests that the holes created through vacancy cascade on the krypton atoms are transferred to the surrounding atoms, and that the singly charged ions are the primary product of the krypton photoabsorption. Charge localization is suggested for the inner-core excited mixed rare-gas clusters from the analysis of the EICO peak width. The MHMI measurements give us direct evidence for the strong charge migration from X-ray absorbing atoms to surrounding atoms. The photon energy dependence of the PSD image for fragment ions suggests that the momentum of the fragment ions depends on the number of charges generated by the vacancy cascade.     

Recombination of U 92 + ions with electrons

Recombination of fully stripped U⁹²⁺ ions with electrons has been investigated at the Experimental Storage Ring (ESR) in Darmstadt. Absolute recombination rate coefficients have been measured for relative energies from 0 to 33 eV. For energies greater than 20 meV the experimental result is well described by the theory for radiative recombination (RR). Below 20 meV the experimental rate increasingly exceeds the RR calculation as observed previously in the recombination of light bare ions as well as of Bi⁸³⁺. This low-energy rate enhancement is shown to scale as Z^2.6 for bare ions, where Z is the atomic number of the ion. The U⁹²⁺ recombination rate enhancement is insensitive to changes of the electron density. Variation of the magnetic guiding field strength from 80 mT to 120 mT resulted in oscillations of the recombination rate at 0 eV. The oscillations are partly attributed to changes of the transverse electron temperature accompanying the change of the magnetic guiding field strength; partly they may be caused by uncompensated small changes of the interaction angle between the two beams. Received 1st March 2001 and Received in final form 20 April 2001     

Electron multiplicity in slow collisions of Ar ions with C

Electron capture by Ar⁸⁺ in collisions with C₆₀ fullerene has been investigated using coincident measurements of the number n of ejected electrons, the mass and charge of multicharged Cr+ ₆₀ recoil ions and their fragments Ci+ m and the final charge state of outgoing projectiles Ar(8-s)+ (). The number of captured electrons r is the sum of the numbers of stabilized and emitted electrons: r = n + s. The ratio n / s decreases by a factor three with s increasing from 1 to 7 showing that the multiply excited states populated by capture of a large number of electrons are rather stable against auto-ionisation. Each kinetic energy spectrum of Ar⁺ and Ar²⁺ projectiles is composed of two peaks which we attribute to collisions “inside” and “outside” the C₆₀ cage. The measured energy shift of the projectile keV is consistent with the corresponding energy loss keV in a carbon foil with an equivalent thickness. Inside collisions are characterized by a strong dissociation of recoil ions into light monocharged fragments and by a high multiplicity of ejected electrons. Received: 25 March 1998 / Received in final form and Accepted: 9 June 1998     

Influence of covalence and anion symmetry on the structure of small metal hydroxide clusters: Sodium versus silver hydroxide

An ab initio study of the Na_n(OH)_n, Na_n(OH)_n-1 ⁺, Ag_n(OH)_n, and Ag_n(OH)_n-1 ⁺ clusters with n up to four is presented. The results of this study show that, in accordance with experimental observations, the sodium hydroxide clusters are almost purely ionic, while the Ag-O bond exhibits a significant covalent character. The perturbation caused by the non-spherical OH^- group relatively to an atomic anion, as well as the influence on structures and energies of the covalent character of the metal-oxygen bond are determined. The appearance of metal-metal bonds in the silver hydroxide clusters is also discussed. Finally, the theoretical results obtained on the Na-OH clusters are compared to experimental results available on the dissociation of the Na_n(OH)_n-1 ⁺ clusters. Received 9 August 1999 and Received in final form 1st December 1999     

Stability and fragmentation of multiply ionized clusters

The stability of neutral, singly and multiply ionized silicon clusters, (N = 2-7, M = 0, , , ), has been investigated using an ab initio density functional method. We show that the fragmentation effect significantly affects the structure of mass-spectra of multiply ionized silicon clusters. For clusters, the clusters with a large fragmentation energy are found to correspond to the high peaks at N = 4 and 6 in mass-spectra. For clusters, a peak at N = 5 in mass-spectra has been predicted to be especially high. Received: 9 June 1997 / Revised: 8 January 1998 / Accepted: 25 February 1998     

Energetics and dynamics of decaying cluster ions

The recent addition of (i) a third sector field to our two sector field mass spectrometer (resulting in a BE1E2 field configuration) and of (ii) a high performance electron gun enables us now to study in detail the time dependence of the kinetic energy release distribution (KERD) over a relatively wide range of cluster ion lifetimes. Using this newly constructed device we have studied here for the first time KERDs and deduced binding energies BEs (using finite heat bath theory) of large rare gas cluster ions (an upper size limit in earlier studies arose from the fact that different naturally occurring isotopes will contribute to a chosen metastable peak when the size exceeds a certain value) and in addition of fullerene ions smaller and larger than (here again contaminating coincidences did not allow such studies earlier). Moreover, high precision KERD measurements for the decay of rare gas dimer ions in conjunction with model calculations (using recently calculated potential energy curves for the rare gas dimer ions) also enable us to obtain information on the dynamics and the mechanisms of the underlying spontaneous decay reactions . In addition, we are also reporting here a novel method (unified breakdown graph method) to determine cluster ion binding energies using a recently constructed tandem mass spectrometer BESTOF allowing us to measure fragmentation patterns arising from the unimolecular decay of molecular cluster ions induced by surface collisions. The fragmentation and reaction patterns of protonated ethanol cluster ions investigated here clearly demonstrate in contrast to some of the earlier cluster ion studies that unimolecular dissociation kinetics determines the formation of product ions in the surface-induced decomposition.     

New approaches to stored cluster ions

Ion traps are wall-less containers which allow the extended storage of selected species. During the storage various interaction steps may be repeatedly applied. To this end no further hardware has to be added - in contrast to beam experiments. In this progress report two examples of recent developments are presented: the experiments have been performed with metal clusters stored in a Penning (ion cyclotron resonance) trap. A new experimental scheme has been developed which allows precision measurements of the dissociation energies of polyatomic species. It has been triggered by investigations on the delayed photodissociation of stored metal clusters. However, the technique is also readily available for application to a broad variety of different species and it is not even restricted to trapping experiments. The second development is more closely connected with ion storage in Penning traps: by application of an electron bath singly charged anionic clusters can be converted into multiply charged species. Subsequently, they are charge selected and investigated with respect to their reaction upon excitation. In particular, preliminary results indicate that dianionic metal clusters emit two electrons upon photoexcitation whereas the singly charged species show dissociation.     

Predictions of geometrical structures and ionization potentials for small barium clusters Ba

The geometrical structure of ground state Ba_n clusters (n =2-14) has been predicted from various types of calculations including two ab initio approaches used for the smaller sizes namely HF+MP2( n =2-6), DFT (LSDA)( n =2-6, 9) and one model approach HF+pairwise dispersion used for all sizes investigated here. The lowest energy configurations as well as some isomers have been investigated. The sizes n =4, 7 and 13 are predicted to be the relatively more stable ones and they correspond to the three compact structures: the tetrahedron, the pentagonal bipyramid and the icosahedron. The growth behavior from Ba₇ to Ba₁₃ appears to be characterized by the addition of atoms around a pentagonal bipyramid leading to the icosahedral structure of Ba₁₃ which is consistent with the observed size-distribution of barium clusters. Values for vertical ionization potentials calculated for n =2-5 at the CI level are seen to be in quite good agreement with recent measures. Received: 14 May 1997 / Received in final form: 2 February 1998 / Accepted: 27 February 1998     

Metastable fragmentation of silver bromide clusters

The abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most abundant species are Ag_nBr_{n - 1} ⁺ and Ag_nBr_{n + 1} ^- and Ag₁₄Br₁₃ ⁺ is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-halide ionic clusters. From a certain size, Ag_nBr_{n - 1} ⁺ is no more the main series, and Ag_nBr _{n - 2, 3} ⁺ series become almost as important. The fast fragmentation induced by a UV laser makes the cations lose more bromine than silver ions and lead to more silver-rich clusters. Negative ions mass spectra contain also species with more silver atoms than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new experimental method. The large majority of the cations release mainly a neutral Ag₃Br₃ cluster. These decay channels are in full agreement with our recent ab initio DFT calculations, which show that Ag⁺-Ag⁺ repulsion is reduced due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr)₃ and to quasi-planar cyclic structures of (AgBr)_n clusters up to n = 6. We have shown that these two features may be extended to other silver halides, to silver hydroxides (AgOH)_n, and to cuprous halide compounds. Received 9 November 2000 and Received in final form 25 January 2001     

The power of the small

We review some of the ways clusters offer special kinds of insights both into properties of bulk matter and properties unique to small systems. We then survey some of the tantalizing open questions that lie ahead in cluster science.     

Decay pathways of small gold clusters

The decay pathway competition between monomer and dimer evaporation of photoexcited cluster ions Au ⁺ _n, n = 2-27, has been investigated by photodissociation of size-selected gold clusters stored in a Penning trap. For n > 6 the two decay pathways are distinguished by their experimental signature in time-resolved measurements of the dissociation. For the smaller clusters, simple fragment spectra were used. As in the case of the other copper-group elements, even-numbered gold cluster ions decay exclusively by monomer evaporation, irrespective of their size. For small odd-size gold clusters, dimer evaporation is a competitive alternative, and the smaller the odd-sized clusters, the more likely they decay by dimer evaporation. In this respect, Au ⁺ ₉ shows an anomalous behavior, as it is less likely to evaporate dimers than its two odd-numbered neighbors, Au ⁺ ₇ and Au ⁺ ₁₁. This nonamer anomaly is typical for copper-group cluster ions M ⁺ ₉ (M = Cu, Ag, Au) and a similar behavior is found in the anionic heptamers M ^- ₇. It is discussed in terms of the well-known electronic shell closing at n _e = 8 atomic valence electrons. Received 2 November 2000     

Dimer dissociation energies of small odd-size clusters

The dimer dissociation energies of gold cluster ions Au ⁺ _n , n = 9, 11, 13, 15 have been determined with an extension of a recently developed model-independent method. Monomer-dimer decay pathway branching ratios provide the energy dependent process which is needed in this method. The measured values are D ₂ ( Au ⁺ ₉ ) = 3.66(8)(9) eV, D ₂ ( Au ⁺ ₁₁ ) = 4.27(11)(8) eV, D ₂ ( Au ⁺ ₁₃ ) = 4.50(9)(7) eV and D ₂ ( Au ⁺ ₁₅ ) = 4.29(10)(6) eV. Received 13 May 2002 / Received in final form 22 July 2002 Published online 24 September 2002 RID="a" ID="a"e-mail: manuel.vogel@uni-mainz.de