Linda Giacomozzi

Threshold Energies for Single Carbon Knockout from Polycyclic Aromatic Hydrocarbons

We have measured absolute cross sections for ultrafast (femtosecond) single-carbon knockout from polycyclic aromatic hydrocarbon (PAH) cations as functions of He–PAH center-of-mass collision energy in the 10–200 eV range. Classical molecular dynamics (MD) simulations cover this range and extend up to 105 eV. The shapes of the knockout cross sections are well-described by a simple analytical expression yielding experimental and MD threshold energies of EthExp = 32.5 ± 0.4 eV and EthMD = 41.0 ± 0.3 eV, respectively. These are the first measurements of knockout threshold energies for molecules isolated in vacuo. We further deduce semiempirical (SE) and MD displacement energies, i.e., the energy transfers to the PAH molecules at the threshold energies for knockout, of TdispSE = 23.3 ± 0.3 eV and TdispMD = 27.0 ± 0.3 eV. The semiempirical results compare favorably with measured displacement energies for graphene (Tdisp = 23.6 eV).

Failure of hydrogenation in protecting polycyclic aromatic hydrocarbons from fragmentation

A recent study of soft x-ray absorption in native and hydrogenated coronene cations, C_24H_12+m^+ m=0–7, led to the conclusion that additional hydrogen atoms protect (interstellar) polycyclic aromatic hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014)]. The present experiment with collisions between fast (30–200 eV) He atoms and pyrene (C_16H_10+m^+, m=0, 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.

Non-statistical fragmentation of large molecules in collisions with atoms

Non-statistical fragmentation processes are important when Polycyclic Aromatic Hydrocarbon (PAH) molecules, fullerenes, or other large molecules collide with atoms at center- of-mass energies from a few tens to a few hundreds of eV. The typical result is the prompt, billiard-ball-like knockout of single atoms (CHx-loss). This is distinct from the well-known statistical fragmentation patterns of these molecules, which are dominated by H- and C2H2-loss for PAHs and C2-loss for fullerenes. We have explored the role of non-statistical fragmentation of PAHs and fullerenes in a series of experimental and theoretical studies. In general, the yield of non-statistical fragments depends sensitively on their stability against secondary statistical fragmentation following knockout.

DESIREE electrospray ion source test bench and setup for collision induced dissociation experiments

In this paper, we give a detailed description of an electrospray ion source test bench and a single-pass setup for ion fragmentation studies at the Double ElectroStatic Ion Ring ExpEriment infrastructure at Stockholm University. This arrangement allows for collision-induced dissociation experiments at the center-of-mass energies between 10 eV and 1 keV. Charged fragments are analyzed with respect to their kinetic energies (masses) by means of an electrostatic energy analyzer with a wide angular acceptance and adjustable energy resolution.

Knockout driven fragmentation of porphyrins

We have studied collisions between tetraphenylporphyrin cations and He or Ne at center-of-mass energies in the range 50-110 eV. The experimental results were interpreted in view of density functional theory calculations of dissociation energies and classical molecular dynamics simulations of how the molecules respond to the He/Ne impact. We demonstrate that prompt atom knockout strongly contributes to the total destruction cross sections. Such impulse driven processes typically yield highly reactive fragments and are expected to be important for collisions with any molecular system in this collision energy range, but have earlier been very difficult to isolate for biomolecules.

Measuring lifetimes of Polycyclic Aromatic Hydrocarbon fragments

We investigate collisions of Polycyclic Aromatic Hydrocarbon cations with noble gases at center-of- mass energies close to 100 eV and below. Charged fragments are stored in a new version of the electrostatic ion beam trap ConeTrap. After storage for different well-defined times we extract the ions and use a reflectron based time-of-flight mass spectrometer to analyse the ion mass distributions. This will give information on secondary decay channels and the lifetime of the initially trapped fragment.

Fragmentation studies of Hydrogenated-Pyrene Polycyclic Aromatic Hydrocarbons in collisions with He

We have studied the fragmentation of Pyrene or hydrogenated Pyrene cations (C16H+10+x with x = 0, 5, 6 and 16) in collision with He. We find that the carbon backbone fragmentation cross section increases with the number of H atoms added. This suggests that hydrogenation does not protect PAHs in, e.g., harsh interstellar environments.

Collision Induced Dissociation of PAHs and Biomolecules

We have performed an extensive set of experiments with focus on collisions between PAH or biomolecular cations and He atoms at center-of-mass energies around 100 eV. In this energy range, non-statistical fragmentation processes are important.