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Updated: Apr 7, 2026

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On Covalent N₂H₆: A High-Energy, Non-Lewis, Local Minimum That May (Not) Exist.

Kelling J Donald¹, George Ruthven¹

¹Department of Chemistry, Gottwald Center for the Sciences, University of Richmond, Richmond, Virginia 23173, United States.

The Journal of Physical Chemistry. A

|April 6, 2026

Summary

Ammonia (NH3) can form a high-energy dimer, hexahydridodinitrogen (N2H6), through covalent bonding. However, its stability is sensitive to computational methods, and dissociation is likely, challenging current chemical bonding theories.

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Published on: December 6, 2021

Area of Science:

Quantum Chemistry
Theoretical Chemistry
Chemical Bonding

Background:

Saturated period 2 p-block molecules (e.g., CH4, NH3, H2O) typically do not dimerize via covalent bonds due to full octets.
Investigating exceptions to established chemical principles drives scientific advancement.

Purpose of the Study:

To computationally examine ammonia (NH3) as a potential exception to the rule of non-dimerization.
To probe the existence and characteristics of a covalently bound dimer of ammonia, hexahydridodinitrogen (N2H6).

Main Methods:

Computational chemistry methods were employed to study the potential energy surface of ammonia pairs.
Analysis focused on identifying stable minima, specifically a local singlet minimum with D3d symmetry.

Main Results:

A high-energy, covalently bound hexahydridodinitrogen (N2H6) minimum was identified on the ammonia pair's potential energy surface.
The stability and location of this dimer are highly sensitive to the computational model chemistry used, particularly post-Hartree-Fock methods.
No other examined period two p-block singlet dimer pairs formed stable covalent minima.
The N2H6 species exhibits a tendency towards dissociation through competing channels.

Conclusions:

While a hexahydridodinitrogen (N2H6) dimer can be computationally identified, its realization is challenged by its high energy and propensity for dissociation.
The observed energy lowering, enhanced by Rydberg bonding, suggests potential for novel chemical bonding interactions.
This study encourages further exploration of the boundaries of chemical bonding.