Formation of HCN+ in collisions of N+ and N2+ with a self-assembled propanethiol surface on gold.

Collisions of N+ and N2+ with C3 hydrocarbons, represented by a self assembled monolayer of propanethiol on a polcrystalline gold surface, were investigated by experiments over the incident energy range between 5 eV and 100 eV. For N+, formation of HCN+ is observed at incident energies of projectile ions as low as 20 eV. In the case of N2+ projectile ions, the yield of HCN+ increased above zero only at incident energies of about 50 eV. This collision energy in the laboratory frame corresponds to an activation energy of about 3 eV to 3.5 eV. In the case of N+ projectile ions, the yield of HCN+ was large for most of the incident energy range, but decreased to zero at incident energies below 20 eV. This may indicate a very small energy threshold for the surface reaction between N+ and C3 hydrocarbons of a few tenths of an eV. Such a threshold for the formation of HCN+ may exist also for collisions of N+ with an adsorbed mixture of hydrocarbon molecules.

A high sensitivity, high resolution tandem mass spectrometer to research low-energy, reactive ion-surface interactions.

The device described is the combination of two mass spectrometers, with a surface sample placed between them. Its aim is to allow for detailed research on low-energy ion-surface interactions, involving and triggering surface chemistry. This task is fulfilled by a carefully chosen geometry: Projectile ions from an electron impact source are mass-per-charge selected using a quadrupole. Such continuous bombardment allows for good control of the surface condition. Species emerging from the collisions are focused onto a beam and analyzed using a purpose-built orthogonal pulsing time-of-flight mass spectrometer. Neutral species can be post-ionized using a second electron impact source. Neutral gases can be adsorbed to the surface from the gas phase in a controlled manner, using a feedback-controlled pressure regulator. In order to minimize the discrimination of secondary ions, the distance from the surface to the analyzing mass spectrometer system was kept as short as possible and the acceptance angle of the lens system as large as possible. This increased the sensitivity five orders of magnitude compared to its predecessor. The rigorous use of computer aided design software is responsible for the successful commissioning of the new device. This article describes first which parameters can be measured or controlled. Then, these are linked to the physical processes that occur in reactive ion-surface interactions. Next, the design goal and the design implementation are presented. In the end, a performance comparison, measurements of hydrogen surface chemistry with extensive use of isotope labeling, and measurements of post-ionized beryllium are presented.

Ionization of Ammonia Nanoices with Adsorbed Methanol Molecules.

Large ammonia clusters represent a model system of ices that are omnipresent throughout the space. The interaction of ammonia ices with other hydrogen-boding molecules such as methanol or water and their behavior upon an ionization are thus relevant in the astrochemical context. In this study, ammonia clusters (NH3) N with the mean size N̅ ≈ 230 were prepared in molecular beams and passed through a pickup cell in which methanol molecules were adsorbed. At the highest exploited pickup pressures, the average composition of (NH3) N(CH3OH) M clusters was estimated to be N: M ≈ 210:10. On the other hand, the electron ionization of these clusters yielded about 75% of methanol-containing fragments (NH3) n(CH3OH) mH+ compared to 25% contribution of pure ammonia (NH3) nH+ ions. On the basis of this substantial disproportion, we propose the following ionization mechanism: The prevailing ammonia is ionized in most cases, resulting in NH4+ core solvated most likely with four ammonia molecules, yielding the well-known "magic number" structure (NH3)4NH4+. The methanol molecules exhibit a strong propensity for sticking to the fragment ion. We have also considered mechanisms of intracluster reactions. In most cases, proton transfer between ammonia units take place. The theoretical calculations suggested the proton transfer either from the methyl group or from the hydroxyl group of the ionized methanol molecule to ammonia to be the energetically open channels. However, the experiments with selectively deuterated methanols did not show any evidence for the D+ transfer from the CD3 group. The proton transfer from the hydroxyl group could not be excluded entirely or confirmed unambiguously by the experiment.