Charge Transfer Dynamics in Gas-Phase Radical Reactions

Charge transfer in gas‐phase radical reactions encompasses the transient migration of electrons between ionic species and neutral molecules, leading to the formation of reactive radical intermediates. These processes play a pivotal role in fields as diverse as atmospheric chemistry, combustion science, astrochemistry and plasma diagnostics. When a charged particle—such as a cation or radical ion—encounters a neutral molecule, the relative potential energy surfaces of the colliding partners may align to permit electron transfer. This event can yield a newly ionised species and a neutral radical, which then undergoes subsequent rearrangements, fragmentation or further reactions. Experimental investigations often employ collision‐induced emission spectroscopy or mass spectrometric methods to detect luminescent fragments and map out kinetic energy dependencies, while high‐level ab initio calculations provide insight into potential energy curves, non‐adiabatic couplings and transient complex lifetimes. A detailed understanding of these dynamics is essential for modelling reaction networks in planetary atmospheres, interpreting spectroscopic signatures in interstellar media and optimising plasma‐based technologies for materials processing and radiation therapy.

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Charge Transfer Dynamics in Gas-Phase Radical Reactions publication trend

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Technical terms

Charge transfer: The process by which an electron moves from one species (donor) to another (acceptor) during a collision.

Radical: A highly reactive species containing an unpaired electron, formed when a bond is homolytically cleaved or by electron transfer.

Collision‐induced emission spectroscopy: An experimental technique that detects light emitted by excited fragments following collisional excitation or charge transfer.

Transient complex: A short‐lived intermediate formed when two reacting species momentarily bind before undergoing electron transfer or fragmentation.

Dissociation cross‐section: A measure of the probability that a collision will lead to molecular fragmentation, often energy‐dependent and observed as resonance features.

References

1. Charge Transfer, Complexes Formation and Furan Fragmentation Induced by Collisions with Low-Energy Helium Cations. International Journal of Molecular Sciences (2019).
2. Neutral Dissociation of Pyridine Evoked by Irradiation of Ionized Atomic and Molecular Hydrogen Beams. International Journal of Molecular Sciences (2021).