Relativistic Effects in Superheavy Element Chemistry

As atomic number increases beyond 100, electrons experience nuclear Coulomb fields of such strength that their velocities approach the speed of light, giving rise to pronounced relativistic phenomena. These effects alter orbital energies and shapes, most notably contracting s and p1/2 shells while expanding and destabilising d and f orbitals. The resulting shifts in valence‐shell structure modify chemical bonding, redox potentials and bulk properties in ways that often defy periodic‐table expectations. For example, strong spin–orbit coupling in element 118 is predicted to narrow its band gap sufficiently that solid oganesson behaves more like a semiconductor than an inert gas. In group 12, copernicium is calculated to adopt liquid‐like properties under ambient conditions, contrasting with the metallic character of its lighter congeners. Accurate treatment of relativistic effects thus proves essential both for reliable theoretical predictions and for guiding one‐atom‐at‐a‐time experimental probes of transactinide chemistry. This interplay between quantum electrodynamic corrections, Dirac‐based electronic‐structure methods and state‐of‐the‐art synthesis underscores the transformative role of relativity in defining the frontier of the periodic table.

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Relativistic Effects in Superheavy Element Chemistry publication trend

The graph below shows the total number of articles in relativistic effects in superheavy element chemistry across all publications each year (not limited to Nature Index journals).

Technical terms

Dirac equation: A relativistic wave equation for electrons, accounting for spin and negative‐energy states.

Spin–orbit coupling: The interaction between an electron’s spin and its orbital motion, leading to energy‐level splitting.

Scalar‐relativistic effect: The increase in electron mass and contraction of orbitals due to high nuclear charge, treated without spin–orbit terms.

Quantum electrodynamic effect: Corrections arising from electron–photon interactions, such as self‐energy and vacuum polarisation, significant in high‐Z atoms.

References

1. Pushing the limits of the periodic table — A review on atomic relativistic electronic structure theory and calculations for the superheavy elements. Physics Reports (2023).
2. Copernicium: A Relativistic Noble Liquid. Angewandte Chemie International Edition (2019).
3. Oganesson Is a Semiconductor: On the Relativistic Band‐Gap Narrowing in the Heaviest Noble‐Gas Solids. Angewandte Chemie International Edition (2019).