J. Kočišek

Uptake of atmospheric molecules by ice nanoparticles: Pickup cross sections

Uptake of several atmospheric molecules on free ice nanoparticles was investigated. Typical examples were chosen: water, methane, NO(x) species (NO, NO(2)), hydrogen halides (HCl, HBr), and volatile organic compounds (CH(3)OH, CH(3)CH(2)OH). The cross sections for pickup of these molecules on ice nanoparticles (H(2)O)(N) with the mean size of N≈260 (diameter ~2.3 nm) were measured in a molecular beam experiment. These cross sections were determined from the cluster beam velocity decrease due to the momentum transfer during the pickup process. For water molecules molecular dynamics simulations were performed to learn the details of the pickup process. The experimental results for water are in good agreement with the simulations. The pickup cross sections of ice particles of several nanometers in diameter can be more than 3 times larger than the geometrical cross sections of these particles. This can have significant consequences in modelling of atmospheric ice nanoparticles, e.g., their growth.

Ionization of large homogeneous and heterogeneous clusters generated in acetylene-Ar expansions: Cluster ion polymerization

Pure acetylene and mixed Ar-acetylene clusters are formed in supersonic expansions of acetylene/argon mixtures and analysed using reflectron time-of-flight mass spectrometer with variable electron energy ionization source. Acetylene clusters composed of more than a hundred acetylene molecules are generated at the acetylene concentration of ≈8%, while mixed species are produced at low concentrations (≈0.7%). The electron energy dependence of the mass spectra revealed the ionization process mechanisms in clusters. The ionization above the threshold for acetylene molecule of 11.5 eV results in the main ionic fragment progression (C2H2)n(+). At the electron energies ≥21.5 eV above the CH+CH(+) dissociative ionization limit of acetylene the fragment ions nominally labelled as (C2H2)nCH(+), n ≥ 2, are observed. For n ≤ 7 these fragments correspond to covalently bound ionic structures as suggested by the observed strong dehydrogenation [(C2H2)n - k × H](+) and [(C2H2)nCH - k × H](+). The dehydrogenation is significantly reduced in the mixed clusters where evaporation of Ar instead of hydrogen can stabilize the nascent molecular ion. The C3H3(+) ion was previously assigned to originate from the benzene molecular ion; however, the low appearance energy of ≈13.7 eV indicates that a less rigid covalently bound structure of C6H6(+) ion must also be formed upon the acetylene cluster electron ionization. The appearance energy of Arn(C2H2)(+) fragments above ≈15.1 eV indicates that the argon ionization is the first step in the fragment ion production, and the appearance energy of Arn≥2(C2H2)m≥2(+) at ≈13.7 eV is discussed in terms of an exciton transfer mechanism.

Energy and charge transfer in ionized argon coated water clusters.

We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H2O)n clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar(+) and water occurs above the threshold; at higher electron energies above ~28 eV, an excitonic transfer process between Ar(+)* and water opens leading to new products Ar(n)H(+) and (H2O)(n)H(+). On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H2O)(n)H2(2+) and (H2O)(n)(2+) ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent.

Velocity map imaging of HBr photodissociation in large rare gas clusters

We have implemented the velocity map imaging technique to study clustering in the pulsed supersonic expansions of hydrogen bromide in helium, argon, and xenon. The expansions are characterized by direct imaging of the beam velocity distributions. We have investigated the cluster generation by means of UV photodissociation and photoionization of HBr molecules. Two distinct features appear in the hydrogen atom photofragment images in the clustering regime: (i) photofragments with near zero kinetic energies and (ii) hot photofragments originating from vibrationally excited HBr molecules. The origin of both features is attributed to the fragment caging by the cluster. We discuss the nature of the formed clusters based on the change of the photofragment images with the expansion parameters and on the photoionization mass spectra and conclude that single HBr molecule encompassed with rare gas snowball is consistent with the experimental observations.

Electron attachment properties of c-C4F8O in different environments

The electron attachment properties of octafluorotetrahydrofuran (c-C4F8O) are investigated using two complementary experimental setups. The attachment and ionization cross sections of c-C4F8O are measured using an electron beam experiment. The effective ionization rate coefficient, electron drift velocity and electron diffusion coefficient in c-C4F8O diluted to concentrations lower than 0.6% in the buffer gases N2, CO2 and Ar, are measured using a pulsed Townsend experiment. A kinetic model is proposed, which combines the results of the two experiments.

Short review on the acetylene photochemistry in clusters: photofragment caging and reactivity

We have investigated solvent effects on acetylene photodissociation in clusters of different sizes and compositions generated in molecular beams: pure acetylene clusters (C2H2) n , 10–200, and mixed (C2H2) m u2009·u2009Rg n (Rgu2009=u2009Ar, Xe) species where the single acetylene molecule or small cluster can be either adsorbed on the surface or embedded inside the rare gas cluster. We review our previous experiments in which the photodissociation dynamics was studied by the H-fragment time-of-flight (TOF) technique, and extend the experiments by measurements with a new velocity map imaging set up. We observe an unusual manifestation of the cage effect leading to a formation of fast hydrogen fragments. Such observation is interpreted as resulting from a two-step process: first, the initially excited molecule is quenched by the cluster cage to a vibrationally hot ground state; then the molecule dissociates upon subsequent photoabsorption from the vibrationally excited state. Thus the faster fragments result from the caging combined with the multiphoton processes. In xenon clusters with acetylene molecules adsorbed on the surface, we have also found evidence for organo-xenon molecule HXeCCH generated in the singlet excited state of a acetylene–xenon complex.

Long-lived transient anion of c-C4F8O

We report partial cross sections for electron attachment to c-C4F8O, a gas with promising technological applications in free-electron-rich environments. The dissociative electron attachment leads to a number of anionic fragments resulting from complex bond-breaking and bond-forming processes. However, the anion with the highest abundance is the non-dissociated (transient) parent anion which is formed around 0.9 eV electron energy. Its lifetime reaches tens of microseconds. We discuss the origin of this long lifetime, the anions strong interactions with other molecules, and the consequences for electron-scavenging properties of c-C4F8O in denser environments, in particular for its use in mixtures with CO2 and N2.

Growth of ice nanoparticles via uptake of individual molecules: pickup cross sections

We present cross sections for pickup of several atmospherically relevant molecules on ice nanoparticles with the 0.5-3 nm diameter range. The experimental values are supported by molecular dynamics simulations and analytical calculations based on long-range cluster-molecule potentials. The cross sections are all considerably larger than the geometrical cross section of nanoparticle and vary significantly for different guest molecules.