Cluster generation in expansions of pure water vapour and of mixtures with carbon dioxide

The condensation of pure superheated water vapour and of a mixture with carbon dioxide in a supersonic jet behind a sonic nozzle has been investigated by the nozzle molecular beam method. The relation of source temperature, pressure, and nozzle diameter necessary for fully developed condensation has been determined for the pure vapour. By using the retarding potential technique, the cluster size distribution function and the dependence of the mean cluster size on the nozzle source conditions have been obtained. Mass-spectrometric measurements of the beam composition in a mixture expansion have revealed the presence of both homogeneous and heterogeneous clusters. The fully developed condensation in CO₂-H₂O mixture was found to begin at a smaller total source pressure than in pure water vapour or carbon dioxide.     

Investigation of a Simple Pickup Method for Doping Molecules into Water Clusters

A capillary pickup method was investigated for doping molecules into water clusters, which were produced by supersonic expansion, and underwent a sticking collision with a crossed beam from the capillary. This method was applied to H₂O clusters in a beam with pickup of DCl, CH₃OH, NH₃, CO₂ and D₂O molecules, however, we found only molecule of DCl can be picked up by water clusters with the capillary configuration in those tested dopants. Meanwhile, two different distances between the capillary to the nozzle were investigated based on the collected mass spectra, and we found that the smaller distance can obtain the stronger mixed cluster intensity.     

Cluster size effect on electron-induced luminescence

As a result of combined measurements of radiation intensity, electronically excited particles density and the density of mass-separated ions formed by a collision of electrons with CO₂, N₂O, H₂O molecules and clusters in intersecting beams it has been found that the process of ejection of electronically excited particles from clusters forms a main contribution to electron-induced luminescence in a mass-spectrum of molecular, fragmented and microcluster ions. The value of this contribution depends on the cluster sizeN. The enhancement of electron-induced luminescence by small clusters (N ? 15) has been found.     

Spectroscopy of large molecules in inert gas clusters

Aromatic hydrocarbons provide nucleation centers for the formation of clusters of inert gases in high-flow supersonic beams. Large clusters of Ar, each containing a single tetracene (T) molecule, were prepared by supersonic expansion of the seeded gas at pressures p = 3000–13000 Torr and interrogated by laser-induced fluorescence spectroscopy Evidence is reported for homogeneous line broadening of large TAr_n clusters prepared at p? 8000 Torr.     

Condensation of Argon,Monosilane and Their Mixtures in a Pulse Free Jet

Pulse supersonic outflow of Ar, SiH₄ and Ar + SiH₄ gas mixture (where monosilane is a small admixture) was studied experimentally by the method of molecular beam mass-spectrometry. Using argon as an example we have shown that condensation processes at the quasi-stationary region of a pulse flow and within a stationary jet are similar. In the flows of pure gases clusters of argon and silane (hydrogenated silicon) and in the mixture argon – silane complexes were registered. The dependencies of the intensities of monomer and cluster ions on stagnation pressure were investigated. It was shown that in the mixture jet at low stagnation pressures the condensation process with the formation of monosilane clusters takes place and at high pressures mixed argon-silane complexes are formed. The parameters of flow transition into the regime of developed condensation were determined for pure gases and their mixture.     

CO<Subscript>2</Subscript> Cluster Ion Beam,an Alternative Projectile for Secondary Ion Mass Spectrometry

The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO₂ as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO₂ and Ar cluster projectiles (cluster size 1000–5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar₂₀₀₀ and (CO₂)₂₀₀₀ on an organic target also confirm that the CO₂ molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO₂ cluster projectiles is improved by more than a factor of two. The advantage of CO₂ versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure.

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Effective absolute rate constant for the formation of negatively-charged CO2 cluster ions by electron transfer from state-selected Rydberg atoms

We have studied electron transfer from state-selected Ar** (nd) Rydberg atoms to (CO₂) _m clusters for 12≦n≦48. The relative rate constant for the total negative ion formation reaches its maximum forn=21 and decreases towards lower and highern. From an accurate study of Penning ionization of nozzle beams with and without cluster formation we were able to derive the condensed fraction in our (CO₂) _m cluster beam and from a statistical analysis of cluster distributions we obtain an estimate for the absolute value of the effective rate constant for the total negative ion formation, which amounts to (4.5 ± 3) · 10^?8 cm³/s for Ar** (21d).     

Sensitivity enhancement using chemically reactive gas cluster ion beams in secondary ion mass spectrometry (SIMS)

We report for the first time on significant molecular secondary ion yield increases by modifying the chemistry of a water cluster primary ion beam. This was demonstrated using 70-keV ion beams of 0.15 eV/amu. For the neutral drug Bezafibrate, secondary ion yield enhancements ×5–10 were observed when replacing the Ar carrier gas in a water gas cluster ion beam (GCIB) source with a mixture containing 12% CO₂ and 2% O₂ in Ar. For the cationic drug Ranitidine, the ion yield enhancements using the CO₂-containing carrier gas were up to ×20–50 in positive mode and ×2–4 in negative mode. The extent of molecular fragmentation was very similar from both cluster beams. We conclude that additional chemically reactive species are present in the impact zone using the (H₂O/CO₂)_n projectile, which promote the formation of secondary ions of both polarity through projectile impact-induced chemical reactions. This methodology can be applied to further extend the capabilities of high-resolution 3-dimensional mass spectral imaging using reactive GCIB-SIMS.     

Formation and Characterization of Large (Ar) n , (N2) n , and Mixed (Ar) n (N2) m van der Waals Clusters Produced by Supersonic Expansion

This paper reports the formation and characterization of large (Ar) _n , (N₂) _n , and mixed binary (Ar) _n (N₂) _m van der Waals clusters produced at room temperature in the process of supersonic expansion. The average cluster size is determined by the buffer gas induced beam-broadening technique. For both Ar and N₂ clusters, power variations of the average cluster size with the gas stagnation pressure P ₀ give size scaling as . The average cluster sizes of argon vary from 2950 to more than 30900 atoms per cluster with the argon gas stagnation pressures ranging from 4 to 14 bars, and of nitrogen vary from 600 to more than 10400 molecules per cluster with the nitrogen gas stagnation pressures ranging from 8 to 38 bars. The mixed binary (Ar) _n (N₂) _m cluster is produced by supersonic expansion of an Ar–N₂ mixture. The large mixed binary (Ar) _n (N₂) _m clusters with the average sizes n + m between 1000 and 16000 are obtained. In coexpansion of Ar–N₂ mixture, we find that the argon concentration becomes higher in the beam than before the expansion. This finding is discussed and may be helpful for further insight into the phenomenon of clustering.     

Diffraction and vibrational dynamics of large clusters from He atom scattering

The vibrational dynamics of large Ar _n clusters from n=30 to n=4500 is investigated by measuring the energy loss of He atoms in a high resolution scattering experiment. The clusters are generated by adiabatic expansion through conical nozzles and contain a distribution of cluster sizes. The He supersonic nozzle beam provides a resolution of better than 1 meV. The results are compared with calculated spectral density functions for single cluster sizes and bulk phonon spectra.     

Electron bombardment fragmentation of size selected molecular clusters

(CO₂) _n , (NO) _n and (NH₃) _n clusters are generated in a supersonic molecular beam and size selected by scattering from an He beam. By measurements of angular dependent mass spectra, TOF distributions and the angular dependence of the scattered signal quantitative information on the fragmentation probability by electron impact is derived. The van der Waals systems (CO₂) _n and (NO) _n appear only at masses which are simply multiples of the monomer mass. The preferred cluster ion is the monomer ion for all investigated cluster sizes withn=2 to 4. The fragment pattern for the quasi-hydrogen bonded (NH₃) _n -cluster shows, beside a large number of fragment masses, a preference for protonated ions. The results are explained in terms of simple models based on the structural change from the neutral to the ionized configuration and the fragmentation pattern of the monomer followed by ionmolecule reactions.     

The gas phase “matrix isolation” spectroscopy of CH3F

We report infrared photodissociation spectra for Ne, Ar, Kr, N₂ and CH₄ clusters which contain CH₃F chromophores. The CH₃Fv ₃ mode is excited with a line tunable CO₂ laser. Mass spectrometer detection of changes in the cluster beam intensity serve to partially distinguish the spectra of different size neutral clusters. Many spectra consist of rather broad, inhomogeneous profiles. For intermediate size Ar_nCH₃F clusters a sharp, narrow peak is observed in the spectrum. We assign this peak as due to a cluster in which a central CH₃F molecule is surrounded by at least a full shell of Ar atoms packed in a contracted icosohedral geometry. Because the Ar atoms in a gas phase cluster are unconstrained by an extended crystalline structure, the CH₃F dipole is more fully stabilized (and thus red-shifted) than in a solid matrix. The dependence of the observed spectrum on cluster size is discussed. For comparison, no comparable narrow spectral features are observed in Ar_nC₂H₄ cluster spectra. Clear evidence is also presented that the fragmentation of the neutral clusters upon electron impact ionization is fairly specific. Finally, we note that ionization of Ar_nCH₃F clusters sometimes produces Ar_nF⁺ ions. This is a fragmentation process which does not occur in free CH₃F.     

Average cluster size determination in supersonic beams from angular distribution measurements after scattering by a buffer gas

A method for the determination of average cluster size in supersonic beams is presented. Based on angular distribution broadening of the beams caused by passing through a buffer gas, this method is well suited for in situ determination of the mean cluster size when the apparatus contains a movable detector with sufficient spatial resolution. The shape and width of the beam profile after scattering by a buffer gas are evaluated theoretically as functions of buffer gas pressure and atom-cluster collision cross-section. Experimental results are presented for an argon beam, yielding average cluster sizes between 300 and 7000 atoms depending on the stagnation pressure. Simple criteria to assess the applicability of the method to a given experimental situation are discussed. The average cluster sizes determined in this work agree quite satisfactorily with previously published values for similar beam generation conditions.     

Reactions of O with CO van der Waals molecules and clusters

The reaction of O(³ P) with COR _m clusters to produce electronically excited CO₂ was studied under molecular beam conditions. It was found that the spectrum of the chemiluminescence produced extended from the blue all the way to the near infrared. The dependence of the total emission intensity on stagnation pressure was investigated for (CO) _m as well as for COR _m , R=He, Ne, Ar, N₂, CO₂ and SO₂. The low pressure data indicate that small (CO) _m polymers are more efficient than clusters of CO with other species in inducing the chemiluminescent reaction. The larger CO-rare gas clusters, however, exhibited larger reaction cross-sections than those of the CO polymers. Rare gas clusters ofm≧5, on the other hand have successively smaller cross sections for reaction. The reactivity of the CO₂ and SO₂ clusters seems to peak at aboutm=1 and then decreases for larger species. An equilibrium model for cluster formation was proposed and it was found capable of explaining and simulating the experimental observations. Contrary to what was reported from afterglow experiments, no barrier for the reaction was detected.     

Cluster chemical ionization and deuterium exchange mass spectrometry in supersonic molecular Beams

A cluster-based chemical ionization method has been developed that produces protonated molecular ions from molecules introduced through a supersonic molecular beam interface. Mixed clusters of the analyte and a clustering agent (water or methanol) are produced in the expansion region of the beam, and are subsequently ionized by “fly through” electron impact (EI) ionization, which results in a mass spectrum that is a combination of protonated molecular ion peaks together with the conventional EI fragmentation pattern. The technique is presented and discussed as a tool complementary to electron impact ionization in supersonic molecular beams. Surface-induced dissociation on a rhenium oxide surface is also applied to simplify the mass spectra of clusters and reveal the analyte spectrum. The high gas flow rates involved with the supersonic molecular beam interface that enable the easy introduction of the clustering agents also have been used to introduce deuterating agents. An easy-to-use, fast, and routine on-line deuterium exchange method was developed to exchange active hydrogens (NH, OH). This method, combined with electron impact ionization, is demonstrated and discussed in terms of the unique information available through the EI fragmentation patterns, its ability to help in isomer identification, and possible applications with fast gas chromatography-mass spectrometry in supersonic molecular beams.     

Laser beam profiles in SF6: direct evidence for beam distortion

High-resolution spatial profile measurements of a CO₂ TEA laser beam propagating through SF₆/Ar mixtures indicate that IR multiple photon absorption measurements averaged over the entire laser beam spatial distribution can be in error by at least a factor of two, implying that accurate measurements require an optically thin sample. This is due to the intensity dependence of the absorption cross section.     

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.     

Collision induced fragmentation of mass-selected (CO2) n + clusters

The collisional velocity dependence of the cross sections for fragmentation of mass-selected (CO₂) _n ⁺ (n+2...7) clusters in collisions with Ar atoms is presented. Interesting structure can be observed in the cross sections which indicate that the collision occurs between the Ar atom and one CO₂ molecule within the cluster. The results may be explained by assuming that the collision leads to either vibrational excitation of a loosely bound CO₂ monomer which then leaves the cluster or excitation of the entire cluster to a dissociative state.     

On the history of cluster beams

The methods to produce and investigate cluster beams have been developed primarily with the use of permanent gases. A summary is given of related work carried out at Marburg and Karlsruhe. The report deals with the effect of carrier gases on cluster beam production; ionization, electrical acceleration and magnetic deflection of cluster beams; the retarding potential mass spectrometry of cluster beams; cluster size measurement by atomic beam attenuation; reflection of cluster beams at solid surfaces; scattering properties of⁴He and³He clusters; the application of cluster beams in plasma physics, and the reduction of space charge problems by acceleration of cluster ions.     

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.