Gas-Phase Ion Chemistry and Thermochemical Properties

Gas-phase ion chemistry explores the formation, transformation and reactivity of charged species isolated in the vapour phase, providing fundamental insights into bond strengths, reaction dynamics and energy landscapes. Central to this field are measurements of ionisation energies and bond dissociation energies, which together define reaction thermochemistry and determine pathways under kinetic versus thermodynamic control. Techniques such as mass spectrometry, laser spectroscopy and tunable synchrotron radiation enable precise determination of enthalpies of formation, electron affinities and reaction barriers. Complementary theoretical methods—including ab initio and density functional theory—yield potential energy surfaces and predict rate coefficients across temperature regimes. Advances in producing internally cold ions, resolving rotational–vibrational structure and manipulating reaction conditions have expanded the scope of gas-phase studies into areas as diverse as atmospheric ion chemistry, astrochemical modelling, plasma processing and materials synthesis. A robust thermochemical database supports predictive modelling of catalytic cycles, ion–molecule clustering and the stability of exotic species in interstellar and industrial environments.

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Gas-Phase Ion Chemistry and Thermochemical Properties publication trend

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

Technical terms

Bond dissociation energy: The energy required to homolytically cleave a specific chemical bond in an isolated molecule in the gas phase.

Ionisation energy: The minimum energy needed to remove an electron from a neutral atom or molecule to form a gas-phase cation.

Autoionisation: The spontaneous ejection of an electron from an excited molecular state without the emission of a photon.

Vibrational anharmonicity: The deviation of a molecule’s vibrational behaviour from the ideal harmonic oscillator, leading to unequal spacing between energy levels.

Solvation shell: The immediate layer of solvent molecules or ligands interacting directly with an ion or cluster in the gas phase.

References

1. f-Block reactions of metal cations with carbon dioxide studied by inductively coupled plasma tandem mass spectrometry. Physical Chemistry Chemical Physics (2023).
2. Solvation of cationic copper clusters in molecular hydrogen. Physical Chemistry Chemical Physics (2023).
3. Gas-phase vibrational spectroscopy of the dysprosium monoxide molecule and its cation. Physical Chemistry Chemical Physics (2024).