The sequence to hydrogenate coronene cations: A journey guided by magic numbers

TL;DR

This study combines experimental and quantum chemistry methods to reveal a site-specific hydrogenation sequence in coronene cations, uncovering magic numbers of attached hydrogen atoms that influence stability and cosmic hydrogen formation.

Contribution

It demonstrates the existence of magic numbers in hydrogenated coronene cations and elucidates the hydrogenation pathway with implications for space chemistry and hydrogen storage.

Findings

Magic numbers of 5, 11, and 17 hydrogen atoms confirmed experimentally.

Hydrogenation follows a site-specific sequence with high transition barriers.

Insights into PAH hydrogenation's role in cosmic H2 formation.

Abstract

The understanding of hydrogen attachment to carbonaceous surfaces is essential to a wide variety of research fields and technologies such as hydrogen storage for transportation, precise localization of hydrogen in electronic devices and the formation of cosmic H2. For coronene cations as prototypical Polycyclic Aromatic Hydrocarbon (PAH) molecules, the existence of magic numbers upon hydrogenation was uncovered experimentally. Quantum chemistry calculations show that hydrogenation follows a site-specific sequence leading to the appearance of cations having 5, 11, or 17 hydrogen atoms attached, exactly the magic numbers found in the experiments. For these closed-shell cations, further hydrogenation requires appreciable structural changes associated with a high transition barrier. Controlling specific hydrogenation pathways would provide the possibility to tune the location of hydrogen attachment and the stability of the system. The sequence to hydrogenate PAHs, leading to PAHs with magic numbers of H atoms attached, provides clues to understand that carbon in space is mostly aromatic and partially aliphatic in PAHs. PAH hydrogenation is fundamental to assess the contribution of PAHs to the formation of cosmic H2.