Intermolecular Potential Energy Surfaces and Complexes

Intermolecular potential energy surfaces (PES) constitute a foundational concept in physical chemistry, mapping the energy of a molecular assembly as a function of nuclear coordinates. By delineating the location and depth of minima, PES analyses reveal the preferred geometries and binding energies of weakly bound complexes. These surfaces underpin our understanding of non-covalent interactions—dispersion, electrostatics, induction and, in specific cases, charge transfer—and guide predictions of rovibrational spectra, collisional cross-sections and reaction dynamics. Modern computational strategies combine high-level ab initio methods with analytic fitting schemes to represent PES for systems ranging from rare-gas dimers and halogen-bonded adducts to aromatic clusters. Quantum effects, such as zero-point energy and tunnelling, often modulate the topology of the surface, especially at cryogenic temperatures or in low-energy collisions. Insights gleaned from PES inform areas as diverse as atmospheric and interstellar chemistry, the design of novel materials, host–guest recognition in supramolecular systems and the control of stereodynamics in gas-phase reactions.

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Intermolecular Potential Energy Surfaces and Complexes publication trend

The graph below shows the total number of articles in intermolecular potential energy surfaces and complexes across all publications each year (not limited to Nature Index journals).

Technical terms

Potential energy surface (PES): A multidimensional representation of the potential energy of a molecular assembly as a function of nuclear positions.

Van der Waals forces: Weak, non-covalent interactions arising from induced dipole–induced dipole attractions that stabilise many molecular complexes.

Quantum Theory of Atoms in Molecules (QTAIM): A topological approach to analyse electron density, identifying bond critical points and quantifying interaction character.

Symmetry-Adapted Perturbation Theory (SAPT): A method that decomposes intermolecular interaction energy into physically meaningful components (electrostatics, exchange, induction, dispersion).

Diffusion Monte Carlo (DMC): A stochastic quantum Monte Carlo technique used to compute ground-state energies, including zero-point effects, on high-dimensional PES.

References

1. (Ro)vibrational Spectroscopic Constants, Lifetime and QTAIM Evaluation of Fullerene Dimers Stability. Molecules (2023).
2. Rare gas-naphthalene interaction: Intermolecular potentials and clusters’ structures. Chemical Physics Letters (2021).
3. Molecular Oxygen Trimer: Multiplet Structures and Stability. ChemPhysChem (2023).