Cluster Ion Reactivity in Gas-Phase Metal Complexes

Cluster ion reactivity in the gas phase examines how size-selected aggregates of metal atoms interact with small molecules when isolated from surfaces and solvents. These systems provide atomic-scale models for heterogeneous catalysis, revealing the influence of cluster size, elemental composition and electronic state on binding, activation and reaction pathways. Mass spectrometric selection coupled with infrared spectroscopy enables structural characterisation of coordination shells and ligand geometries, while computational methods map reactive potential energy surfaces and elucidate reaction mechanisms. Studies encompass the adsorption and dissociation of molecules such as CO, NO and N₂O, illustrating how cooperative binding and electronic effects drive bond activation. Insights from these investigations inform the rational design of nanoscale catalysts for environmental remediation, energy conversion and synthetic chemistry, highlighting the global significance of understanding cluster-mediated transformations under isolated conditions.

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Cluster Ion Reactivity in Gas-Phase Metal Complexes publication trend

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Technical terms

Cluster ion: A gas-phase aggregate of metal atoms carrying a net charge, used to model surface reactions at atomic scale.

Infrared photodissociation spectroscopy: A technique that induces fragmentation of mass-selected ions by resonant infrared absorption to probe structural features.

Coordination shell: The immediate set of ligands or adsorbates directly bound to the metal atoms within a cluster.

Thermal desorption spectrometry: A method for measuring the temperatures at which adsorbed species detach from clusters, yielding adsorption energies.

Reactive potential energy surface: The multidimensional energy landscape that describes how potential energy varies with atomic arrangements during a reaction.

Density functional theory: A quantum-mechanical computational approach to predict electronic structure, energetics and reaction pathways of clusters.

References

1. Probing the binding and activation of small molecules by gas-phase transition metal clusters via IR spectroscopy. Chemical Society Reviews (2023).
2. Zooming in on the initial steps of catalytic NO reduction using metal clusters. Physical Chemistry Chemical Physics (2022).
3. Free electron laser infrared action spectroscopy of nitrous oxide binding to platinum clusters, Pt n (N 2 O) +. Physical Chemistry Chemical Physics (2020).
4. Size-dependent reactivity of Rh cationic clusters to reduce NO by CO in the gas phase at high temperatures. Physical Chemistry Chemical Physics (2024).