Gas Phase Ion Chemistry and Spectroscopy Dynamics

Gas-phase ion chemistry explores the intrinsic reactivity of charged species in isolation, free from solvent effects, while spectroscopy dynamics focuses on real-time monitoring of electronic and vibrational transitions alongside fragmentation pathways. State-of-the-art experiments employ techniques such as electrospray and laser ionisation, ion traps coupled with tandem mass spectrometry, infrared, ultraviolet and vacuum-ultraviolet action spectroscopy, as well as synchrotron-based X-ray methods. Together, these approaches elucidate fundamental processes including proton transfer, cluster formation, photodissociation and electron rearrangement. The insights gained underpin astrochemical models of prebiotic synthesis, inform atmospheric and environmental ion chemistry, guide the design of gas-phase catalytic analogues and advance biomolecular structural analysis.

Research from Nature Portfolio

Recent studies have demonstrated that low-energy ion collisions with β-alanine clusters efficiently drive peptide-bond formation, producing up to tetrapeptides via consecutive water elimination steps. This reveals plausible prebiotic routes to oligomeric peptides under space-like conditions.

Advanced X-ray photoelectron spectroscopy of isolated uracil clusters, supported by ab initio and molecular dynamics simulations, has resolved the roles of hydrogen bonding, π-stacking and dispersion interactions in shifting core-level binding energies, thereby clarifying mechanisms of nucleic acid fragmentation.

Investigations of high-energy superoxide anion collisions with benzene have uncovered a novel anion-driven reaction pathway in which sudden double ionisation leads to a covalent benzene-oxide dication that evolves into benzene-diol conformers, opening new perspectives on gas-phase oxidation dynamics.

Gas Phase Ion Chemistry and Spectroscopy Dynamics publication trend

The graph below shows the total number of articles in gas phase ion chemistry and spectroscopy dynamics across all publications each year (not limited to Nature Index journals).

Technical terms

Collision-induced dissociation (CID): fragmentation of ions through collisions with inert gas molecules to reveal structural and energetic information.

Action spectroscopy: technique in which ion absorption of photons is inferred from the yield or pattern of resulting fragments, enabling spectral measurements of transient species.

Photoelectron–photoion coincidence (PEPICO): simultaneous detection of ejected electrons and fragment ions to correlate absorption events with specific dissociation channels.

Potential energy surface (PES): multidimensional representation of the energy of a molecular system as a function of nuclear positions, guiding reaction dynamics.

Intersystem crossing: non-radiative transition between electronic states of different spin multiplicity, often mediating photochemical pathways.

References

1. Polypeptide formation in clusters of β-alanine amino acids by single ion impact. Nature Communications (2020).
2. Unravelling molecular interactions in uracil clusters by XPS measurements assisted by ab initio and tight-binding simulations. Scientific Reports (2020).
3. Gas Phase Oxidation of Carbon Monoxide by Sulfur Dioxide Radical Cation: Reaction Dynamics and Kinetic Trend With the Temperature. Frontiers in Chemistry (2019).
4. Unexpected benzene oxidation in collisions with superoxide anions. Scientific Reports (2021).
5. VUV Photofragmentation of Chloroiodomethane: The Iso-CH2I–Cl and Iso-CH2Cl–I Radical Cation Formation. The Journal of Physical Chemistry A (2020).
6. Ionization and Photofragmentation of Isolated Metalloporphyrin Cations Investigated by VUV Action Spectroscopy**. Chemistry - A European Journal (2021).