Study of V-V transfer in CD2Cl2 by laser-induced fluorescence experiments

Vibrational energy transfer between the fundamentals of CD₂Cl₂ is studied by laser-induced fluorescence experiments. The data obtained confirm the result and interpretation of former acoustic experiments which indicated an inefficient energy exchange between the lowest vibrational mode and the upper modes. The pτ value obtained for this V-V process is 60 μs Torr. Energy transfer between the upper modes is more efficient and the corresponding pτ values are smaller than 4 μs Torr for the modes investigated in this work.     

Mass spectroscopic study of some novel water clusters: (H2O) n + ;n>3

A near atmospheric pressure ion source with a β-emitter as electron source is used to inject ions into a supersonic water expansion. Cluster ions of the structure (H₂O)⁺ _n have been observed forn up to 8. Forn>3 these cluster ions cannot be obtained by ionization of water clusters in vacuum, but they can be grown in the cold environment of a supersonic beam. Extremely clean conditions are necessary for the observation of these cluster ions. The data can be explained by assuming that the local potential minimum calculated for the (H₂O) _n ⁺ ,n=2, potential hypersurface exists also forn>2. The model developed to explain these data is similar to that proposed for ionized rare gas clusters.     

A REMPI study of solvation of small Hg n clusters by polar molecules

Free Hg _n (DME) _m clusters (where DME=dimethyl-ether,n=1, 2, 3,m=1÷5) formed in a supersonic expansion were studied by the REMPI (Resonance-Enhanced Multi-Photon Ionization) technique. A large decrease of ionization energies due to solvation of Hg _n clusters is observed. Preliminary results are discussed in terms of different equilibrium configurations of the electronic ground, excited and ionic states of clusters.     

Size effects in the solid phase transition of SF6 clusters

The structure of SF₆ clusters produced in a free jet expansion is studied by electron diffraction methods. A solid phase transition is known to occur when clusters are warmed up by changing several experimental conditions in the expansion of a Ne + SF₆ mixture. In the present study, the total stagnation pressure and the SF₆ mole fraction are varied in order to understand how these parameters influence the structural state of the clusters and further to observe the phase transition for different cluster sizes. When the stagnation pressurep ₀ is larger than about 10 bar, a given mole fraction results in clusters with identical structure and probably identical temperature. Whenp ₀ is decreased below 10 bar, identical structures are found for lower and lower mole fractions. This structural behaviour suggests that for small clusters, containing less than about 500 molecules, the transition steps occur at temperatures lower than those observed for larger clusters. The possibility of detecting a temperature variation in the diffraction patterns of small cubic clusters is discussed.     

Production of large sodium clusters (Nax,.x⩽65) by seeded beam expansions

Seeded beam expansions of high-temperature sodium vapour in helium, neon, argon, krypton and nitrogen carrier gases are examined. Photoionization coupled with mass spectroscopic detection is used to determine beam constituents. Contrary to non-seeded supersonic expansions, in which the abundance of sodium clusters observed decreases exponentially with increasing cluster size, large abundances of higher clusters (Na_x, x ?65) are observed. Maxima centered at m/z = 161, m/z = 437 and m/z = 874 occur under certain conditions.     

Rotational and vibrational temperatures of naphthalene in a naphthalene-argon supersonic jet

In the $\text{A}$¹B_2u-$\text{X}$¹A_g system of naphthalene in a supersonic jet, rotational contour calculations show rotational temperatures of 2–60 K for argon carrier gas pressures of 1520-120 Torr. The b_1u vibration v₂₄ shows a high vibrational temperature which corresponds to the seeding temperature for pressures <400 Torr.     

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.     

Analysis of the reactivity of small cobalt clusters

The electronic structures of small cobalt clusters have been calculated within the local spin density approximation using the LCAO method. The calculations were done for simple geometries with the optimized number of interatomic bonds, and both for the bond length of the cobalt dimer and the bulk metal. The Fermi energy is found to be smaller for Co _N clusters withN=3, 4, 5 andN>10 than for the other ones. The variation of the Fermi energy with the cluster size correlates in a striking way with the observed H₂ tendency for chemisorption as found for cobalt clusters in a supersonic beam. Furthermore, the magnetic moments are somewhat smaller for these active clusters. In addition the lowest unoccupied levels of majority spin appear close to the highest occupied levels of minority spin which is not the case for the inert clusters.     

Photoelectron spectroscopy of jet-cooled aluminium cluster anions

Aluminium cluster anions (Al _n ^? ) are produced by laser vaporization without additional ionization and cooled by supersonic expansion. Photoelectrons from mass-identified anion bunches (n=2...25) are detached by laser light (hv=3.68 eV) and undergo energy analysis in a magnetic bottle-type time-of-flight spectrometer. The measurements provide information about the electronic excitation energies from ionic ground states to neutral states of the clusters. In contrast to bulk aluminium these cluster photoelectron spectra partially have well-resolved bands which originate from low-lying excited bands. For small clusters, especially the aluminium dimer and trimer, quantum-chemical calculations will be compared to the measurements. The electron affinity size dependence of larger clusters shows conclusive evidence for “shell” effects.     

Vacuum-UV photoemission-photoion coincidence spectroscopy of neutral metal atom clusters

A newly developed photoion-photoelectron Vacuum-UV coincidence spectrometer has been coupled to a supersonic metal atom cluster beam source and has been used to investigate the electronic structure of isolated mercury clusters in the size range from 1 to 110 at several selected discrete excitation energies between 11.3 and 7.1 eV. Excitation of the van der Waals cluster Hg₁₀ at the center of the strongD _3/2-autoionization line at 10.7 eV yields a photoelectron kinetic energy distribution between 0 and 2.5 eV indicating the population of Hg₁₀ ionic states, which are also accessible by threshold ionization.     

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.     

Ion attachment to Van der Waals clusters

Mixed ionized clusters have been produced in a supersonic nozzle beam experiment by attachment of stagnant cations (i.e. NO⁺ and Xe⁺) to neutral van der Waals clusters (i.e.Ar _n ) within a Nier type ion source. This new ionization technique leads to less fragmentation than electron impact ionization and the measured cluster distributions exhibit icosahedral shell and subshell closures which have not been detected in the case of electron impact of Ar _n -clusters ionization so far. Additionally, the obtained appearance energies and metastable fractions give insight into the production mechanism and the stability of the resulting ions.     

Calculation of the electronic properties of neutral and ionized divalent-metal clusters

The electronic properties of neutral and ionized divalent-metal clusters have been studied using a microscopic theory, which takes into account the interplay between van der Waals (vdW) and covalent bonding in the neutral clusters, and the competition between hole delocalization and polarization energy in the ionized clusters. By calculating the ground-state energies of neutral and ionized Hg _n clusters, we determine the size dependence of the bond character and the ionization potentialI _p (n). For neutral Hg _n clusters we obtain a transition from van der Waals to covalent behaviour at the critical sizen _c ～10–20 atoms. Results forI _p (Hg _n ) withn≤20 are in good agreement with experiments, and suggest that small Hg _n ⁺ clusters can be viewed as consisting of a positive trimer core Hg ₃ ⁺ surrounded byn?3 polarized neutral atoms.     

The singlet nπ* states of para-benzoquinone

The vibronic nπ* singlet spectra of p-benzoquinone-h₄ and p-benzoquinone-d₄ have been observed in a supersonic jet and some as yet unknown excited state fundamentals in the vapor phase have been assigned. The electric dipole forbidden, magnetic dipole allowed origin of the ¹B_1g ← ¹A_g transition is observed at 20045 cm^?1. The origin of the¹A_u ← ¹A_g, transition has been indirectly determined at 19991 cm^?1 from the vibronic excitation spectra. Neither shows a deuterium shift.     

The influence of shells,electron thermodynamics,and evaporation on the abundance spectra of large sodium metal clusters

Measurements of the mass abundance spectra of sodium clusters containing up to 600 atoms are presented. The clusters are produced in a seeded supersonic expansion of Ar or Kr gas, and the spectra are obtained by a time-of-flight technique. The sawtooth features in the spectra are interpreted as evidence of a regular spherical shell structure with magic numbers,N ₀, scaling approximately with the cube root of the number of sodium atoms. Altogether twelve shell closings are observed,N ₀=2, 8, 20, 40, 58, 92, 138, 196, 260, 344, 440 and 558. There is also a pronounced odd-even staggering all the way up toN=70. The experimentally observed intensity changes for the clusters around the magic numbers are discussed in terms of the electronic free energy,F(N), calculated at finite temperature, and the second differences of the free energy Δ₂ F(N)=F(N?1)?2F(N)+F(N+1). The processes behind the non-uniform abundance distributions, and the thermodynamics of finite electron systems with non-uniform level spacings are discussed on this basis.     

Excited state spectroscopy of para di-substituted benzenes in a supersonic beam using resonant two photon ionization

Excited state vibronic spectra of p-aminophenol, p-cresol, p-fluoroaniline, p-fluorophenol, hydroquinone and p-toluidine have been obtained using resonant two photon ionization supersonic beam mass spectrometry. Despite marked similarities in the spectra, notable differences exist and different para polyatomic substituents in the same molecule show vibronic evidence of their real molecular symmetry of C_2ν. Expansion of the ring is also noted upon excitation in all cases. Further, it is now evident that the assignment of some vibronic bands historically interpreted as sequence structure must be reconsidered since molecules like hydroquinone are mixtures of cis and trans and others have a vibronic structure arising from the polyatomic nature of the substituents (cƒ. CH₃).     

Inception of Acetic Acid/Water Cluster Growth in Molecular Beams

The influence of carboxylic acids on water nucleation in the gas phase has been explored in the supersonic expansion of water vapour mixed with acetic acid (AcA) at various concentrations. The sodium‐doping method has been used to detect clusters produced in supersonic expansions by using UV photoionisation. The mass spectra obtained at lower acid concentrations show well‐detected Na⁺?AcA(H₂O)_n and Na⁺?AcA₂(H₂O)_n clusters up to 200 Da and, in the best cooling expansions, emerging Na⁺?AcA_m(H₂O)_n signals at higher masses and unresolved signals that extend beyond m/e values >1000 Da. These signals, which increase with increasing acid content in water vapour, are an indication that the cluster growth taking place arises from mixed water–acid clusters. Theoretical calculations show that small acid–water clusters are stable and their formation is even thermodynamically favoured with respect to pure water clusters, especially at lower temperatures. These findings suggest that acetic acid may play a significant role as a pre‐nucleation embryo in the formation of aerosols in wet environments.     

Molecular structure of van der Waals complex of o- and m-methylaniline with CF3Cl, CF3H, CF4 and CH4 studied by laser induced fluorescence spectroscopy and ab initio calculations

The excitation LIF spectra of van der Waals complexes of o- and p-methylaniline and CF₃Cl, CF₃H, CH₄ and CF₄ in a supersonic free jet are reported. The spectra show a resolved structure characteristic due to the internal rotational transitions of the methyl group. The equilibrium geometries in the ground state of the complexes have been calculated at MP2/6-31+G^∗ level of calculation and the intermolecular interaction have been discussed.     

Fragmentation dynamics of ammonia cluster ions after single photon ionisation

A reflecting time of flight mass spectrometer (RETOF) is used to study unimolecular and collision induced fragmentation of ammonia cluster ions. Synchrotron radiation from the BESSY electron storage ring is used in a range of photon energies from 9.08 up to 17.7 eV for single photon ionisation of neutral clusters in a supersonic beam. The threshold photoelectron photoion coincidence technique (TPEPICO) is used to define the energy initially deposited into the cluster ions. Metastable unimolecular decay (µs range) is studied using the RETOF's capacity for energy analysis. Under collision free conditions the by far most prominent metastable process is the evaporation of one neutral NH₃ monomer from protonated clusters (NH₃) _{n ? 2}NH ₄ ⁺ . Abundance of homogeneous vs. protonated cluster ions and of metastable fragments are reported as a function of photon energy and cluster size up ton=10.     

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.