Spectroscopic Studies of Hydrogen-Bonded Molecular Clusters

Spectroscopic investigations of hydrogen-bonded molecular clusters have matured into a cornerstone of molecular science, offering precise insights into the nature and dynamics of intermolecular interactions. By probing clusters ranging from simple water dimers to complex organic assemblies, researchers employ techniques such as rotational spectroscopy, infrared photodissociation and far-infrared action spectroscopy to resolve structural conformations, vibrational modes and tunnelling phenomena. These studies reveal how hydrogen bonds govern cluster geometry, influence energy landscapes and mediate dynamical processes including proton transfer and surface wetting. High-resolution Fourier transform microwave and chirped-pulse methods capture rotational constants with sub-megahertz accuracy, while infrared and far-infrared approaches illuminate intermolecular vibrations and weak binding regimes. Time-resolved pump–probe infrared spectroscopy further delineates ultrafast solvation and migration pathways. Coupled experimental–computational frameworks, notably Born–Oppenheimer molecular dynamics and dispersion-corrected density functional calculations, reconcile measured spectra with theoretical potential energy surfaces. Collectively, these advances underpin our understanding of atmospheric chemistry, interstellar ice processes, materials wetting and biomolecular hydration, highlighting the global relevance of hydrogen-bond spectroscopy across disciplines.

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Spectroscopic Studies of Hydrogen-Bonded Molecular Clusters publication trend

The graph below shows the total number of articles in spectroscopic studies of hydrogen-bonded molecular clusters across all publications each year (not limited to Nature Index journals).

Technical terms

Hydrogen bond: An attractive interaction between a hydrogen atom covalently bound to an electronegative donor (e.g. O–H or N–H) and an electronegative acceptor atom, critical to cluster stability and dynamics.

Rotational spectroscopy: Measurement of discrete rotational transitions of gas-phase molecules, yielding precise molecular geometries and interatomic distances.

Fourier transform microwave spectroscopy: A high-resolution method that records broadband microwave emission from rotating molecules to determine rotational constants with sub-MHz precision.

Infrared photodissociation (IRPD) spectroscopy: A technique in which cluster ions absorb tunable infrared photons until dissociation, allowing vibrational mode identification in mass-selected complexes.

Far-infrared action spectroscopy: Probing of low-frequency intermolecular vibrations by monitoring an action signal (e.g. fragmentation) induced by far-infrared excitation, sensitive to weak binding interactions.

References

1. Quantum Tunneling Facilitates Water Motion across the Surface of Phenanthrene. Journal of the American Chemical Society (2023).
2. Wetting of a Hydrophobic Surface: Far-IR Action Spectroscopy and Dynamics of Microhydrated Naphthalene. The Journal of Physical Chemistry Letters (2023).
3. Internal Energy Dependence of the Pyrrole Dimer Cation Structures Formed in a Supersonic Plasma Expansion: Charge-Resonance and Hydrogen-Bonded Isomers. The Journal of Physical Chemistry A (2024).