Electron bombardment induced fragmentation of size selected neutral (D2O) n clusters

The fragmentation behaviour of size selected neutral (D₂O) _n clusters withn4 after ionization with 70 eV electrons is subject of this work. Size selection by scattering the cluster beam from a He target beam in combination with a quadrupole mass filter and time resolved measurements at specific laboratory angles enables us to determine the neutral precursor masses of the detected ions. The measured fragment pattern is dominated by deuterated ions of the form (D₂O) _n–x D⁺ withx1. The dimer fragmentation which leads with a probability of 62.5% to the D₃O⁺ ion and with 37.5% to D₂O⁺ can be explained by fast intracluster ion-molecule reactions of charged monomer fragments reacting with the partner molecule. For larger clusters the fragmentation process can be rationalised by the creation of an initially highly excited D₃O⁺ (D₂O) _x complex which is stabilized by evaporating additional monomer units with the main fragment channel (D₂O)D⁺ forn=3 and (D₂O)₂D⁺ forn=4. With increasing cluster size an increasing tendency of evaporation of more than one water monomer unit has been observed.     

Collisional energy transfer and fragmentation of size selected CO2 clusters

Carbon dioxide clusters are generated in a supersonic molecular beam and size selected by scattering from a He beam. By analyzing the measured time-of-flight spectra as a function of the deflection angle, differential energy loss spectra for (CO₂)₂ — He are obtained which show a rotational rainbow structure with a maximal energy transfer of ΔE/E=0.4. This result is compatible with the slipped parallel structure of dimer but not with theT-shaped geometry. The scattering analysis is also used to derive information about the pressure dependence of cluster formation and the fragmentation by electron impact ionisation. The latter process leads preferably to the monomer product ion CO ₂ ⁺ with a small but finite probability for other ionic channels.     

Electron bombardment induced fragmentation of substituted oxathiolanes

The mass spectral fragmentation patterns of 1,3-oxathiolane and 2-, 4-, and 5-substituted oxathiolanes have been recorded. The various fragments have been identified by high-resolution mass spectrometry when appropriate. Of the five possible modes of ring cleavage to produce two- and three-atom fragments only two modes are actually observed. The mode of fragmentation of the 1,3-oxathiolane ring differs from that proposed for 1,3-dioxalane and in all probability occurs in multistep processes.     

IR-photodissociation of size selected molecular clusters and their structures

Infrared photodissociation spectra of (CH₃NH₂) _n clusters were measured fromn=2 ton=6 near the monomer absorption of the C-N stretching mode at 1044 cm^?1 using a cw-CO₂ laser. The clusters were size-selected by scattering from a helium beam. The spectrum of cold dimers shows a red (1038 cm^?1) and a blue (1048 cm^?1) shifted peak which is attributed to the non-equivalent position of the C-N in the open dimer structure. The larger clusters exhibit only one peak between 1045.4 cm^?1 and 1046.0 cm^?1 caused by the equivalent position of the C-N in the cyclic structures of the larger clusters. Structure calculations confirm these results. Secondly, the mixed complexes C₂H₄-CH₃COCH₃ and C₂H₄-(CH₃COCH₃)₂ were investigated. The dimer spectrum, measured around the monomer frequency of the out-of-plane bending mode of C₂H₄ at 949 cm^?1, shows two peaks at 946.2 cm^?1 and 961.3 cm^?1. This splitting is attributed to two different isomers that are found in configuration calculations. A similar behaviour is found for the trimer.     

Electron impact fragmentation of size-selected krypton clusters

Clusters of krypton are generated in a supersonic expansion and size selected by deflection from a helium target beam. By measuring angular distributions for different fragment masses and time-of-flight distributions for fixed deflection angles and fragment masses, the complete fragmentation patterns for electron impact ionization at 70 eV are obtained from the dimer to the heptamer. For each of the neutral Kr(n) clusters studied, the main fragment is the monomer Kr(+) ion with a probability f(n)(1) > 90%. The probability of observing dimer Kr(2)(+) ions is much smaller than expected for each initial cluster size. The trimer ion Kr(3)(+) appears first from the neutral Kr(5), and its fraction increases with increasing neutral cluster size n, but is always much smaller than that of the monomer or dimer. For neutral Kr(7), all possible ion fragments are observed, but the monomer still represents 90% of the overall probability and fragments with n > 3 contribute less than 1% of the total. Aspects of the Kr(n) cluster ionization process and the experimental measurements are discussed to provide possible reasons for the surprisingly high probability of observing fragmentation to the Kr(+) monomer ion.     

Electron impact ionization of size selected hydrogen clusters (H2)N: ion fragment and neutral size distributions

Clusters consisting of normal H2 molecules, produced in a free jet expansion, are size selected by diffraction from a transmission nanograting prior to electron impact ionization. For each neutral cluster (H2)(N) (N=2-40), the relative intensities of the ion fragments Hn+ are measured with a mass spectrometer. H3+ is found to be the most abundant fragment up to N=17. With a further increase in N, the abundances of H3+, H5+, H7+, and H9+ first increase and, after passing through a maximum, approach each other. At N=40, they are about the same and more than a factor of 2 and 3 larger than for H11+ and H13+, respectively. For a given neutral cluster size, the intensities of the ion fragments follow a Poisson distribution. The fragmentation probabilities are used to determine the neutral cluster size distribution produced in the expansion at a source temperature of 30.1 K and a source pressure of 1.50 bar. The distribution shows no clear evidence of a magic number N=13 as predicted by theory and found in experiments with pure para-H2 clusters. The ion fragment distributions are also used to extract information on the internal energy distribution of the H3+ ions produced in the reaction H2+ + H2-->H3+ +H, which is initiated upon ionization of the cluster. The internal energy is assumed to be rapidly equilibrated and to determine the number of molecules subsequently evaporated. The internal energy distribution found in this way is in good agreement with data obtained in an earlier independent merged beam scattering experiment.     

Chemisorption and chemical reactions on size selected clusters

Low energy ion beam techniques have been used to perform a detailed study of the reactions of Al ₂₅ ⁺ and Si ₂₅ ⁺ with a range of simple molecules (D₂, CH₄, O₂, C₂H₄, CO and N₂). The reactions were studied over a center of mass collision energy range from 0.2eV up to 7eV. Activation barriers for chemisorption onto the clusters were deduced from the experimental results. The activation barriers for chemisorption on Al ₂₅ ⁺ and Si ₂₅ ⁺ are generally similar and show a qualitative correlation with the electronic properties of the reactant molecule. However, the products of the chemical reactions of Al ₂₅ ⁺ and Si ₂₅ ⁺ which result from cluster fragmentation are quite different. Si ₂₅ ⁺ shows a tendency to undergo fission as observed in a number of recent studies of the dissociation of the bare clusters.     

The fragment molecular orbital and systematic molecular fragmentation methods applied to water clusters

Two electronic structure methods, the fragment molecular orbital (FMO) and systematic molecular fragmentation (SMF) methods, that are based on fragmenting a large molecular system into smaller, more computationally tractable components (fragments), are presented and compared with fully ab initio results for the predicted binding energies of water clusters. It is demonstrated that, even when explicit three-body effects are included (especially necessary for water clusters due to their complex hydrogen-bonded networks) both methods present viable, computationally efficient alternatives to fully ab initio quantum chemistry.     

Dynamic and quantum size effects in molecular clusters

The evolution of thermodynamic, dynamic and quantum size effects in clusters is expected to contribute towards the merging between microscopic and macroscopic points of view in molecular, surface and bulk phenomena.     

The fragmentation and isomerization of internal energy selected acetaldehyde molecular cations

The fixed wavelength photoelectron—photoion coincidence technique has been employed to study the fragmentation behaviour of excited acetaldehyde molecular cations with internal energies up to 7 eV. The recorded breakdown curves of the parent ion as well as the C₂H₃O⁺, CHO⁺ and CH₃⁺ fragment ions enable to reject state specific fragmentation behaviour of the title compound into the CHO⁺ and CH₃⁺ fragment ion channels. The present data give evidence of a fast isomerization of the CH₃CHO⁺ cation from its first electronically excited state ā(²A″) to the oxirane cation in its electronical ground state X?(²B₂).     

IR double resonance experiments with size selected clusters for identification of isomers

Infrared photodissociation spectra of (CH₃OH) _n clusters (n=2, 3 and 6) and the mixed dimer C₂H₄ · CH₃COCH₃ are presented. The clusters are generated in a supersonic jet expansion and size selected by scattering from a helium atomic beam combined with mass spectrometric detection. Continuous CO₂-lasers are used to vibrationally excite the molecules in the cluster leading to rapid dissociation of the complex. Various dissociation peaks that are found in single-laser dissociation spectra can be assigned unambigously in a pump-probe experiment with two lasers to either different isomers (acetone-ethene dimer) or splitted lines of one isomer (methanol hexamer). For size distributions, the method is able to select contributions of single masses which is demonstrated for mixtures of methanol dimers and trimers.     

Analysis of fragmentation data and molecular orbital calculations of small argon ion clusters

Distributions of argon clusters (Ar _n ⁺ wheren=1–27) obtained in a molecular beam/time-of-flight system were analyzed in order to assess the influence of fragmentation. The results from rudimentary pseudopotential molecular calculations were calculated to predict the most stable structures and stabilities for the smaller argon ion sized clusters (Ar _n ⁺ wheren=3−9).     

Optical spectroscopy on size selected gold clusters deposited in rare gas matrices

We report on the successful “soft-landing” of size selected Au trimers in solid Krypton matrices. The Au cations are produced by sputtering, mass-selected in a quadrupole mass spectrometer, co-deposited with Krypton on a cooled CaF₂ substrate, and neutralized by low energy electrons. The deposition of low kinetic energy cations (10 eV) gives rise to strong excitation bands, detected by the emitted fluorescence light, which are unambiguously attributed to Au trimers. The deposition and fragmentation process is qualitatively discussed.     

Theory of fragmentation of metal clusters

The theory of shell correction developed for discussing fissing of heavy nuclei is applied to symmetric fragmentation of charged metal clusters. Assuming the effective potential of an anisotropic harmonic oscillator, we calculate the shell correction. We also calculate the energy of deformed charged droplets in the two-dimensional parameter space describing the deformation of droplets such as elongation and neck formation. The symmetric fragmentation of microclusters of alkali and noble metals is discussed.     

Electron and nuclear dynamics of molecular clusters in ultraintense laser fields. III. Coulomb explosion of deuterium clusters

In this paper we present a theoretical and computational study of the energetics and temporal dynamics of Coulomb explosion of molecular clusters of deuterium (D2)n/2 (n = 480 - 7.6 x 10(4), cluster radius R0 = 13.1 - 70 A) in ultraintense laser fields (laser peak intensity I = 10(15) - 10(20)W cm(-2)). The energetics of Coulomb explosion was inferred from the dependence of the maximal energy EM and the average energy Eav of the product D+ ions on the laser intensity, the laser pulse shape, the cluster radius, and the laser frequency. Electron dynamics of outer cluster ionization and nuclear dynamics of Coulomb explosion were investigated by molecular dynamics simulations. Several distinct laser pulse shape envelopes, involving a rectangular field, a Gaussian field, and a truncated Gaussian field, were employed to determine the validity range of the cluster vertical ionization (CVI) approximation. The CVI predicts that Eav, EM proportional to R0(2) and that the energy distribution is P(E) proportional to E1/2. For a rectangular laser pulse the CVI conditions are satisfied when complete outer ionization is obtained, with the outer ionization time toi being shorter than both the pulse width and the cluster radius doubling time tau2. By increasing toi, due to the increase of R0 or the decrease of I, we have shown that the deviation of Eav from the corresponding CVI value (Eav(CVI)) is (Eav(CVI) - Eav)/Eav(CVI) approximately (toi/2.91tau2)2. The Gaussian pulses trigger outer ionization induced by adiabatic following of the laser field and of the cluster size, providing a pseudo-CVI behavior at sufficiently large laser fields. The energetics manifest the existence of a finite range of CVI size dependence, with the validity range for the applicability of the CVI being R0 < or = (R0)I, with (R0)I representing an intensity dependent boundary radius. Relating electron dynamics of outer ionization to nuclear dynamics for Coulomb explosion induced by a Gaussian pulse, the boundary radius (R0)I and the corresponding ion average energy (Eav)I were inferred from simulations and described in terms of an electrostatic model. Two independent estimates of (R0)I, which involve the cluster size where the CVI relation breaks down and the cluster size for the attainment of complete outer ionization, are in good agreement with each other, as well as with the electrostatic model for cluster barrier suppression. The relation (Eav)I proportional to (R0)I(2) provides the validity range of the pseudo-CVI domain for the cluster sizes and laser intensities, where the energetics of D+ ions produced by Coulomb explosion of (D)n clusters is optimized. The currently available experimental data [Madison et al., Phys. Plasmas 11, 1 (2004)] for the energetics of Coulomb explosion of (D)n clusters (Eav = 5 - 7 keV at I = 2 x 10(18) W cm(-2)), together with our simulation data, lead to the estimates of R0 = 51 - 60 A, which exceed the experimental estimate of R0 = 45 A. The predicted anisotropy of the D+ ion energies in the Coulomb explosion at I = 10(18) W cm(-2) is in accord with experiment. We also explored the laser frequency dependence of the energetics of Coulomb explosion in the range nu = 0.1 - 2.1 fs(-1) (lambda = 3000 - 140 nm), which can be rationalized in terms of the electrostatic model.     

Statistical fragmentation of hot atomic metal clusters

Fragmentation processes of highly excited neutral and charged atomic metal clusters are studied in the framework of an equilibrium statistical model. In the particular case of hot (near and above melting) neutral and charged sodium clusters of 100 and 200 atoms, a microcanonical Metropolis sampling is used to compute mass (or charge) correlation functions as a function of the excitation energy. This method allows to take the strong anharmonicities in the internal phonon spectrum realistically into account which are linked to the internal structural changes like melting. It is found that, at high enough excitation energy, the system exhibits a phase transition. This phase transition is specific for fragmenting finite systems. From the shape of the caloric curve one sees that the two phases involved are connected by a van der Waals loop characterizing a first order phase transition. Here we observe an enhanced fission and multifragmentation into two or more charged clusters with more than 10 atoms each. Various fragment correlations are studied.     

Electron impact-induced fragmentation of some aminonitropyridines

The fragmentation behaviour of 18 vicinally substituted aminonitropyridines was studied under electron impact conditions. Tbe decomposition patterns were found to be strongly dependent on the position of substituents. The formation of the aza analogue of carbazole seems to affect considerably the fragmentation of 3-nitro-2-phenylaminopyridine.