Showing papers by "Tilmann D. Märk published in 2018"

Correlated ion and neutral time of flight technique combined with velocity map imaging: Quantitative measurements for dissociation processes in excited molecular nano-systems

Abstract: The combination of the Dispositif d’Irradiation d’Agregats Moleculaire with the correlated ion and neutral time of flight–velocity map imaging technique provides a new way to explore processes occurring subsequent to the excitation of charged nano-systems. The present contribution describes in detail the methods developed for the quantitative measurement of branching ratios and cross sections for collision-induced dissociation processes of water cluster nano-systems. These methods are based on measurements of the detection efficiency of neutral fragments produced in these dissociation reactions. Moreover, measured detection efficiencies are used here to extract the number of neutral fragments produced for a given charged fragment.

Sequential evaporation of water molecules from protonated water clusters: measurement of the velocity distributions of the evaporated molecules and statistical analysis

Abstract: Velocity distributions of neutral water molecules evaporated after collision induced dissociation of protonated water clusters H+(H2O)n≤10 were measured using the combined correlated ion and neutral fragment time-of-flight (COINTOF) and velocity map imaging (VMI) techniques. As observed previously, all measured velocity distributions exhibit two contributions, with a low velocity part identified by statistical molecular dynamics (SMD) simulations as events obeying the Maxwell-Boltzmann statistics and a high velocity contribution corresponding to non-ergodic events in which energy redistribution is incomplete. In contrast to earlier studies, where the evaporation of a single molecule was probed, the present study is concerned with events involving the evaporation of up to five water molecules. In particular, we discuss here in detail the cases of two and three evaporated molecules. Evaporation of several water molecules after CID can be interpreted in general as a sequential evaporation process. In addition to the SMD calculations, a Monte Carlo (MC) based simulation was developed allowing the reconstruction of the velocity distribution produced by the evaporation of m molecules from H+(H2O)n≤10 cluster ions using the measured velocity distributions for singly evaporated molecules as the input. The observed broadening of the low-velocity part of the distributions for the evaporation of two and three molecules as compared to the width for the evaporation of a single molecule results from the cumulative recoil velocity of the successive ion residues as well as the intrinsically broader distributions for decreasingly smaller parent clusters. Further MC simulations were carried out assuming that a certain proportion of non-ergodic events is responsible for the first evaporation in such a sequential evaporation series, thereby allowing to model the entire velocity distribution.

Temperature dependence of dissociative electron attachment to bromo-chlorotoluene isomers: Competition between detachment of Cl- and Br.

Abstract: Dissociative electron attachment to three isomers of bromo-chlorotoluene was investigated in the electron energy range from 0 to 2 eV for gas temperatures in the range of 392-520 K using a crossed electron-molecular beam apparatus with a temperature regulated effusive molecular beam source. For all three molecules, both Cl− and Br− are formed. The ion yields of both halogenides show a pronounced temperature effect. In the case of Cl− and Br−, the influence of the gas temperature can be observed at the threshold peak close to 0 eV. The population of molecules that have some of their out-of-plane modes excited varies strongly in the temperature range investigated, indicating that such vibrations might play a role in the energy transfer towards bond breaking. Potential energy curves for the abstraction of Cl− and Br− were calculated and extrapolated into the metastable domain. The barriers in the diabatic curves approximated in this way agree well with the ones derived from the temperature dependence observe...

Maxwell-Boltzmann versus non-ergodic events in the velocity distribution of water molecules evaporated from protonated water nanodroplets.

Abstract: Measurement of velocity distributions of evaporated water monomers from small mass- and energy-selected protonated water clusters allows probing the extent of thermalization after excitation of these ultimately small nanodroplets. Electronic excitation of a molecule in the cluster is here induced by a single collision with an argon atom in the keV energy range. The measured velocity distributions of the departing neutral molecules exhibit bimodal shapes with a lower-velocity part consistent with a complete redistribution of the deposited energy in the entire cluster and a higher-velocity contribution corresponding to evaporation before complete energy redistribution. Statistical molecular dynamics calculations reproduce the bimodal shape of the velocity distributions by assuming an initial spreading of the excitation energy among all modes, thereby reproducing the lower velocity contribution of the distribution. By contrast, assuming the deposited energy to be initially localized among the modes of a single molecule leads to calculated distributions with two components whose shape is in accordance with the experimental results. The characteristics and the relative abundance of these two contributions in the velocity distributions obtained are presented and discussed as a function of the number of molecules (n = 2-10) in the ionized nanodroplet H+(H2O)n.Measurement of velocity distributions of evaporated water monomers from small mass- and energy-selected protonated water clusters allows probing the extent of thermalization after excitation of these ultimately small nanodroplets. Electronic excitation of a molecule in the cluster is here induced by a single collision with an argon atom in the keV energy range. The measured velocity distributions of the departing neutral molecules exhibit bimodal shapes with a lower-velocity part consistent with a complete redistribution of the deposited energy in the entire cluster and a higher-velocity contribution corresponding to evaporation before complete energy redistribution. Statistical molecular dynamics calculations reproduce the bimodal shape of the velocity distributions by assuming an initial spreading of the excitation energy among all modes, thereby reproducing the lower velocity contribution of the distribution. By contrast, assuming the deposited energy to be initially localized among the modes of a sing...