Photoelectron Spectroscopy in Anionic Complexes

Photoelectron spectroscopy (PES) has become an indispensable tool for elucidating the electronic structure of gas-phase anionic complexes. By irradiating size-selected negative ions with monochromatic photons and measuring the kinetic energy of emitted electrons, PES provides direct access to electron affinities, detachment energies and vibrational fine structure. Advances such as cryogenic ion trapping, velocity-map imaging and high-resolution photoelectron imaging now permit the resolution of conformational isomers and subtle electronic effects arising from multicentre bonding and intramolecular interactions. These capabilities have broadened the scope of PES to encompass biomolecular anions, boron cluster complexes and surface-deposited fragments, yielding quantitative data for fundamental studies of hydrogen-bond networks, redox-active sites and catalytically relevant species. Coupled with state-of-the-art theoretical methods capable of predicting detachment thresholds and Franck–Condon profiles, PES fosters a virtuous cycle of experiment and computation. The resultant insights are driving applications in materials chemistry, bioinorganic redox processes and atmospheric monitoring, where precise knowledge of electron-binding energies underpins the design of novel functional systems.

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Photoelectron Spectroscopy in Anionic Complexes publication trend

The graph below shows the total number of articles in photoelectron spectroscopy in anionic complexes across all publications each year (not limited to Nature Index journals).

Technical terms

Photoelectron spectroscopy (PES): Technique that measures kinetic energy of electrons ejected by photon impact on ions to determine electron-binding energies.

Electron affinity: Energy released when an electron is attached to a neutral or radical species, equivalent to the negative detachment energy of an anion.

Cryogenic negative ion photoelectron spectroscopy: PES variant performed at low temperatures to reduce thermal broadening and resolve fine spectral features of anions.

Conformer: One of several spatial arrangements of atoms in a molecule that can interconvert by rotation about single bonds.

Franck–Condon profile: Distribution of vibrational intensities observed in electronic transitions, reflecting overlap between initial and final vibrational wavefunctions.

References

1. Properties of Gaseous Deprotonated L-Cysteine S-Sulfate Anion [cysS-SO3]−: Intramolecular H-Bond Network, Electron Affinity, Chemically Active Site, and Vibrational Fingerprints. International Journal of Molecular Sciences (2023).