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World desk3 min

Quantum Tunnelling May Make Some Hypothetical Benzene Isomers Impossible to Isolate

A computational study of 73 hypothetical tricyclic benzene isomers predicts that quantum tunnelling destabilizes some candidates—but its finding is not a verdict on every benzene isomer.

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A molecule can look stable in a conventional calculation and still fall apart: nuclei can tunnel through an energy barrier that would block them in a purely classical picture. A 2024 computational study predicts that this effect makes some hypothetical, highly strained benzene isomers intrinsically unstable. It does not show that every unusual benzene structure is impossible, or that the predicted decompositions have been observed in experiments.

What the study examined

Sindy Julieth Rodríguez and Sebastian Kozuch assessed 73 hypothetical tricyclic isomers of benzene, each with the formula C6H6. These are proposed structures with three rings, not a census of every conceivable benzene isomer. The study used computational analysis to examine kinetic stability and nuclear quantum effects, including heavy-atom tunnelling in strained molecular frameworks.

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The key distinction is between a structure that appears to be a local minimum on an energy surface and one that persists long enough to be made, detected, or isolated. A molecule may have a decomposition route separated by an energy barrier; quantum tunnelling can let a nucleus pass through that barrier rather than go over it. If decomposition follows, the candidate may be too short-lived to isolate even if a conventional stability assessment suggested otherwise.

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What outcomes did the authors predict?

The paper separates the candidates into different practical outcomes. Its headline result is that 26% of the previously deemed stable molecules in the studied set are predicted to be completely unsynthesizable because tunnelling drives unimolecular decomposition, even close to absolute zero.

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  • 26%: previously deemed stable candidates predicted to be unsynthesizable because of intrinsic tunnelling instability.
  • Five additional systems: predicted to be detectable, but to degrade slowly.
  • Seven additional supposedly stable systems: predicted to break apart through barrierless mechanisms.

These are distinct categories, not a single count of molecules ruled out by tunnelling. The five predicted to degrade slowly are not described as instantly decomposing, while the seven barrierless cases are assigned a different mechanism. The 26% figure is tied to the study’s set of hypothetical tricyclic benzene isomers, not to all benzene isomers or strained molecules generally.

Why “stable” depends on conditions

Stability is not an unconditional label. Rodríguez and Kozuch explicitly note that a species stable at low temperature can be kinetically unstable at higher temperature. Temperature affects whether and how quickly a molecule decomposes, and a theoretical prediction for one regime should not be turned into a universal claim about the molecule at every temperature.

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It also matters whether stability is thermodynamic or kinetic. Thermodynamic stability concerns the relative favorability of states; kinetic stability concerns how readily a molecule can transform. A structure can be a local minimum and still have a pathway to decomposition. The article’s categories address predicted persistence and practical detectability, rather than proving that a candidate was made or measured.

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How to read the tunnelling threshold

For their detailed tunnelling analysis, the authors selected species with a degradation threshold below 60 kJ mol−1 when zero-point energy was included. They report that preliminary calculations suggested deep tunnelling was negligible above that cutoff. This was a method choice for deciding which candidates to study in detail—not a universal chemical boundary separating stable from unstable molecules.

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What the result does—and does not—establish

The paper, “Heavy-atom tunnelling in benzene isomers: how many tricyclic species are truly stable?”, was published in Chemical Science in 2024. Its conclusion is a computational prediction about a defined collection of hypothetical structures. It is not an experimental demonstration that each candidate decomposes, nor evidence that every unusual benzene isomer is unmakeable.

The authors’ result is therefore best read as a warning about how stability assessments can change when nuclear quantum effects are included. For individual isomer names, lifetimes, or precise conditions, the paper’s tables and supplementary information are needed; the headline percentages alone do not establish those details.

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Read the study in Chemical Science.

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