High-Pressure Chemistry of Molecular Reactions

High-pressure chemistry explores how elevated pressures—often in the gigapascal range—alter the pathways, rates and equilibria of molecular transformations. By compressing reactants in devices such as diamond anvil cells or within mechanochemical setups, researchers can reshape potential energy surfaces, reduce activation volumes and stabilise otherwise transient intermediates. Experimentally, pressure can promote concerted pathways over stepwise routes, shift transition states towards reactants and unlock novel reactivity in small molecules, polymers and coordination complexes. Computational advances—most notably continuum models and hydrostatic compression force fields—now allow detailed mapping of reaction profiles under pressure and prediction of pressure‐induced phase or spin transitions. These insights have broad implications for geochemical cycles, green synthesis of fine chemicals, materials under extreme conditions and the design of pressure‐responsive functional materials.

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High-Pressure Chemistry of Molecular Reactions publication trend

The graph below shows the total number of articles in high-pressure chemistry of molecular reactions across all publications each year (not limited to Nature Index journals).

Technical terms

Activation volume: The difference in partial molar volume between transition state and reactants, indicating how pressure affects the reaction rate.

Potential energy surface: A multidimensional landscape describing the electronic energy of a system as a function of nuclear coordinates.

Pressure–volume (PV) term: The work associated with compressing a system, added to electronic energy in high-pressure continuum models.

Extreme pressure polarizable continuum model (XP-PCM): A theoretical method that simulates hydrostatic compression by embedding molecules in a pressure‐dependent dielectric cavity.

Hydrostatic compression force field (X-HCFF): A mechanochemical approach that applies uniform compressive forces to a molecule’s van der Waals volume to model high-pressure effects.

References

1. Achieving Pressure Consistency in Mechanochemical Simulations of Chemical Reactions Under Pressure. Journal of Computational Chemistry (2025).
2. Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes. ChemPhysChem (2019).
3. High‐Pressure Reaction Profiles and Activation Volumes of 1,3‐Cyclohexadiene Dimerizations Computed by the Extreme Pressure‐Polarizable Continuum Model (XP‐PCM). Chemistry - A European Journal (2022).
4. Studying and exploring potential energy surfaces of compressed molecules: A fresh theory from the extreme pressure polarizable continuum model. The Journal of Chemical Physics (2022).