Fragmentation by electron impact ionization and intracluster reactions of size selected (N2H4) n and (OCS) n clusters

The hydrogen-bonded (N₂H₄) _n clusters and the van der Waals (OCS) _n clusters are size selected in a scattering experiment with a He beam up to the cluster sizen=6. By measuring the angular distributions of the scattered clusters the complete fragmentation pattern of electron impact ionization is obtained. For Hydrazine the two main fragment masses are the protonated species (N₂H₄) _n?1H⁺ and with somewhat weaker intensities also the nominal ion mass (N₂H₄) _n ⁺ . The largest intensity is observed for the monomer ion N₂H ₄ ⁺ to which clusters up ton=5 fragment. For carbonylsulfide, completely different results are obtained. Aside from the fragments of the OCS monomer and the van der Waals cluster fragments (OCS) ₂ ⁺ and (OCS) ₃ ⁺ signals at mass S ₂ ⁺ , S ₃ ⁺ and S₂OCS⁺ are detected. This indicates a fast chemical reaction in the cluster according to: S + OCS → CO + S₂ which occurs for clusters of sizen ≥ 2. Peaks at S ₃ ⁺ and S₂OCS⁺ are seen for the first time forn ≥ 5 according to a further reaction of S₂ in the cluster.     

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.     

Electron impact and single photon ionization cross sections of neutral silver clusters

Neutral silver atoms and small clusters Ag _n (n=1...4) were generated by sputtering, i.e. by bombarding a polycrystalline silver surface with Ar⁺ ions of 5 keV. The sputtered particles were ionized by a crossed electron beam and subsequently detected by a quadrupole mass spectrometer. In alternative to the electron impact ionization, the same neutral species were also ionized by single photon absorption from a pulsed VUV laser (photon energy 7.9 eV), and the photoionization cross sections were evaluated from the laser intensity dependence of the measured signals. By in situ combining both ionization mechanisms, absolute values of the ratio σ _e (Ag _n )/σ _e (Ag) between the electron impact ionization cross sections of silver clusters and atoms could be determined for a fixed electron energy of 46 eV. These values can then be used to calibrate previously measured relative ionization functions. By calibrating the results using literature data measured for silver atoms, we present absolute cross sections for electron impact ionization of neutral Ag₂, Ag₃ and Ag₄ as a function of the electron energy between threshold and 125 eV.     

Electron impact ionization of water-doped superfluid helium nanodroplets: observation of He(H(2)O)(n)(+) clusters

Electron impact mass spectra have been recorded for helium nanodroplets containing water clusters. In addition to identification of both H(+)(H(2)O)(n) and (H(2)O)(n)(+) ions in the gas phase, additional peaks are observed which are assigned to He(H(2)O)(n)(+) clusters for up to n=27. No clusters are detected with more than one helium atom attached. The interpretation of these findings is that quenching of (H(2)O)(n)(+) by the surrounding helium can cool the cluster to the point where not only is fragmentation to H(+)(H(2)O)(m) (where m < or = n-1) avoided, but also, in some cases, a helium atom can remain attached to the cluster ion as it escapes into the gas phase. Ab initio calculations suggest that the first step after ionization is the rapid formation of distinct H(3)O(+) and OH units within the (H(2)O)(n)(+) cluster. To explain the formation and survival of He(H(2)O)(n)(+) clusters through to detection, the H(3)O(+) is assumed to be located at the surface of the cluster with a dangling O-H bond to which a single helium atom can attach via a charge-induced dipole interaction. This study suggests that, like H(+)(H(2)O)(n) ions, the preferential location for the positive charge in large (H(2)O)(n)(+) clusters is on the surface rather than as a solvated ion in the interior of the cluster.     

Electron impact ionization of atomic hydrogen

The role of Coulomb-correlation in electron impact ionization of atomic hydrogen is investigated. Triple differential cross sections are calculated using the first order multiple scattering theory taking into account the propper asymptotic behaviour of the final state wavefunction. A semi-empirical procedure is outlined to choose the effective charges consistent with several physically required limits. A comparison with recent experimental data is made; the observed agreement strongly suggests the importance of asymptotic Coulomb-correlation in ionization even at high energies. The first order approximation used here for the hydrogen case is easily generalizable for ionization of several electron atoms at not too large scattering angles and not too low incident energies.     

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.     

Electron impact ionization of small silver and copper clusters

Using a quadrupole mass spectrometer, relative cross sections for electron impact ionization of neutral Ag _n and Cu _n clusters withn=1 ... 4 have been measured for electron energies between threshold and 125 eV. From the results, the following ionization energies were obtained: Ag₂: 7.26±0.1 eV, Ag₃: 6.19±0.2 eV, Ag₄: 6.33±0.3 eV, Cu₂: 7.46±0.15 eV, Cu₃: 6.14±1.0 eV, Cu₄: 7.00±0.6 eV. With only two exceptions, these values agree with other data published for Ag₂, Cu₂, Cu₃ and Cu₄.     

Electron impact ionization and dissociation of neutral and charged fullerenes

Three different types of electron impact ionization experiments have been performed, involving neutral and charged C₆₀ and C₇₀. 1) We have determined absolute partial ionization cross sections for formation of parent ions C ₆₀ ^z+ and C ₇₀ ^z+ in charge states up to z = 4, and of singly and multiply charged fragments of size n ≥ 44 and n ≥ 50 from C₆₀ and C₇₀ neutral precursors, respectively. 2) Previous appearance energy measurements of C₇₀ have been improved and extended to z = 5; ionization energies are found to depend linearly on the charge state of the precursor, in agreement with theoretical predictions. 3) A beam of mass selected C ₆₀ ²⁺ has been crossed with an intense electron beam; the induced reactions (fragmentation, post- ionization, and dissociative post-ionization) have been analyzed.     

Electron binding motifs of (H2O)n- clusters

It is has been established that the excess electrons in small (i.e., n < or = 7) (H2O)n- clusters are bound in the dipole field of the neutral cluster and, thus, exist as surface states. However, the motifs for the binding of an excess electron to larger water clusters remain the subject of considerable debate. The prevailing view is that electrostatic interactions with the "free" OH bonds of the cluster dominate the binding of the excess electron in both small and large clusters. In the present study, a quantum Drude model is used to study selected (H2O)n- clusters in the n = 12-24 size range with the goal of elucidating different possible binding motifs. In addition to the known surface and cavity states, we identify a new binding motif, where the excess electron permeates the hydrogen-bonding network. It is found that electrostatic interactions dominate the binding of the excess electron only for isomers with large dipole moments, whereas in isomers without large dipole moments polarization and correlation effects dominate. Remarkably, for the network-permeating states, the excess electron binds even in the absence of electrostatic interactions.     

Electron impact ionization efficiency curves of van der Waals clusters

The study of van der Waals clusters is an area of growing interest and is being widely studied for a number of reasons. The measurement of the ionization efficiency (IE) curves have yielded a wealth of information by enabling ionization and appearance energies of ions to be determined which are essential for the calculation of thermochemical data. In the case of van der Waals clusters, the measurement ofIE curves enables one to determine the qualitative trends in the ionization potentials as a function of cluster size. In additionIE curves have also offered valuable insight into ionization related processes occurring in clusters. This paper will cover some of the more recent studies of Penning ionization, exciton induced decay and Coulomb explosion in van der Waals clusters through the use of electron impactIE curves.     

A study of hydrogen bond strengths of neutral water clusters (H2O) n using modified MNDO

Semi-empirical molecular orbital methods proposed up to now seriously fail to describe hydrogen bonded systems associated with (H₂O) _n . A new scheme of parametrization using a semi-empirical method is proposed. We tested hydrogen bonding associated with the water clusters (H₂O) _n . The results are found to be close to ab initio Hartree-Fock quality, indicating a good promise for studying hydrogen-bonding systems other than O-H...O moiety.     

Electron impact ionization mass spectrometry and intramolecular cyclization in 2-substituted pyrimidin-4(3H)-ones

Electron impact ionization mass spectrometry indicates that the behavior of W-unsubstituted pyrirnidin-4-ones with CH₂-R type substitution at C-2 differs from homologs that are N-substituted and/or 2-aryl- or 2-methyl-substituted. A dominant intramolecular cycliza-tion was found to occur between 3ZV (in agreement with the predominance of the 3NH tautomers) and the ortho positions of the aryl moiety in compounds with a CH₂-aryl substitution at C-2. Theoretical calculations with an AMI SCFR method on 2-, 6-, and 2, 6-disubstituted pyrimidin-4-ones support the mass spectrometric observations.     

Single photon ionization of hydrogen bonded clusters with a soft x-ray laser: (HCOOH)x and (HCOOH)y(H2O)z

Pure, neutral formic acid (HCOOH)n+1 clusters and mixed (HCOOH)(H2O) clusters are investigated employing time of flight mass spectroscopy and single photon ionization at 26.5 eV using a very compact, capillary discharge, soft x-ray laser. During the ionization process, neutral clusters suffer little fragmentation because almost all excess energy above the vertical ionization energy is taken away by the photoelectron, leaving only a small part of the photon energy deposited into the (HCOOH)n+1+ cluster. The vertical ionization energy minus the adiabatic ionization energy is enough excess energy in the clusters to surmount the proton transfer energy barrier and induce the reaction (HCOOH)n+1+-->(HCOOH)nH+ +HCOO making the protonated (HCOOH)nH+ series dominant in all data obtained. The distribution of pure (HCOOH)nH+ clusters is dependent on experimental conditions. Under certain conditions, a magic number is found at n=5. Metastable dissociation rate constants of (HCOOH)nH+ are measured in the range (0.1-0.8)x10(4) s(-1) for cluster sizes 4相似文献   

Electron impact ionization of silver clusters Ag n,n≦36

Electron impact ionization of gas phase silver clusters Ag _n ,n≦36 has been achieved in the threshold region. The vertical ionization potentials in this region clearly demonstrate the evidence of shell effects as well as a distinct even-odd oscillation up ton?20. Their general size dependence is somewhat different from that of the alkali metal clusters due to the presence of thed-electrons.     

Infrared spectra of CO2-doped hydrogen clusters, (H2)N-CO2

Clusters of para-H(2) and/or ortho-H(2) containing a single carbon dioxide molecule are studied by high resolution infrared spectroscopy in the 2300 cm(-1) region of the CO(2) ν(3) fundamental band. The (H(2))(N)-CO(2) clusters are formed in a pulsed supersonic jet expansion from a cooled nozzle and probed using a rapid scan tunable diode laser. Simple symmetric rotor type spectra are observed with little or no resolved K-structure, and prominent Q-branch features for ortho-H(2) but not para-H(2). Observed rotational constants and vibrational shifts are reported for ortho-H(2) up to N = 7 and para-H(2) up to N = 15, with the N > 7 assignments only made possible with the help of theoretical simulations. The para-H(2) cluster with N = 12 shows clear evidence for superfluid effects, in good agreement with theory. The presence of larger clusters with N > 15 is evident in the spectra, but specific assignments are not possible. Mixed para- + ortho-H(2) cluster transitions are well predicted by linear interpolation between corresponding pure cluster line positions.     

Scattering of neutral NH3 clusters off LiF(100): angular distributions of NH3 and small clusters

The scattering behavior of neutral ammonia clusters off a LiF(100) surface is studied. Ammonia clusters are produced by a coexpansion of NH₃ and Kr with an average kinetic energy of 48 meV per monomer molecule. Using single photon VUV laser ionization at λ = 118 nm (hv = 10.49 eV) the mass distribution of scattered particles is obtained in a reflecting time-of-flight mass spectrometer. Compared with the incoming cluster beam the average cluster size of the scattered particles is drastically decreased. The angular distribution of NH ₃ ⁺ and NH ₄ ⁺ after scattering reveals a strong inelastic interaction between the clusters and the LiF(100) surface which is described in the context of a thermokinetic model and a phonon excitation along the (001) azimuth of the LiF(100) surface.     

Dissociative ionization of O2 and N2 by electron impact — N+ and O+ kinetic energies and angular distributions

An apparatus containing cross molecular and pulsed electron beams has been used to obtain distributions in kinetic energy and angle of fast (? 0.5 eV) positive ions produced through dissociative ionization of N₂ and O₂ by impact of 50 to 2000 eV electrons. Four main O⁺ ion groups are observed with peak energies of 0.8, 2.0, 3.0, and 5.0 eV. Two main N⁺ groups peaking at 2.0 and 3.0 eV are seen. Angular distributions of both N⁺ and O⁺ ions are essentially isotropic for electron-beam-ion detection angles from 30° to 110°.     

Electron impact ionization mass spectra of lithocholyl amides: Evidence for a C(20) to C(23) rearrangement involving the loss of a C4H9 fragment

Amides of lithocholic acid (3α-hydroxy-5β-cholan-24-oic acid) with 6-aminocaproic acid and 4-aminobutyric acid were prepared and examined by electron impact ionization mass spectrometry. Both these compounds gave an unusual [M ? 57]⁺ fragment. Since the product-ion analysis of [M ? 57]⁺ revealed the presence of fragments corresponding to the intact steroid nucleus in addition to that of the original amino acid (6-aminocaproic acid or 4-aminobutyric acid), we concluded that the integrity of the steroid amide had been retained in this fragment. The absence of this fragment from the product-ion spectrum of [M ? CH₃]⁺ rules out the sequential loss from the molecular ion of 15 + 42 u as the origin of this signal. Mass spectrometry of the 24-¹³C-labelled lithocholylcaproylamide showed the retention of the label in the [M ? 57]⁺ fragment. In contrast, the corresponding compound labelled with deuterium at C(23) showed a significant loss of the label during the formation of this product ion at [M ? 58]⁺. In addition, through a combination of derivatization and tandem mass spectrometry, it was demonstrated that this loss of 57 u represented a rearrangement with the expulsion of a C₄H₉ radical from the side-chain spanning C(20) to C(23) resulting in a truncated steroid-amide fragment. This fragmentation pattern has not been observed in bile acid conjugates with N-α-amino acids.     

Infrared spectra of seeded hydrogen clusters: (paraH2)N - OCS, (orthoH2)N - OCS, and (HD)N - OCS, N = 2 - 7

Infrared spectra of hydrogen-carbonyl sulfide clusters containing paraH2, orthoH2, or HD have been studied in the 2060 cm(-1) region of the C-O stretching vibration. The clusters were formed in pulsed supersonic jet expansions and probed using a tunable infrared diode laser spectrometer. Simple symmetric rotor type spectra were observed and assigned for clusters containing up to N = 7 hydrogen molecules. There was no resolved K structure, and Q-branch features were present for orthoH2 and HD but absent for paraH2. These characteristics can be rationalized in terms of near symmetric rotor structures, very low effective rotational temperatures (0.15 to 0.6 K), and nuclear spin statistics. The observed vibrational shifts were compared with those from recent observations on the same clusters embedded in helium nanodroplets. The observed rotational constants for the paraH2 clusters are in good agreement with a recent quantum Monte Carlo simulation. Some mixed clusters were also observed, such as HD-HD-He-OCS and paraH2 - orthoH2 - OCS.     

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.