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Threshold Photoelectron Spectroscopy, Dissociative Photoionization, and Pyrolysis of Aziridine.

Henry Cardwell^1,2, Domenik Schleier³, Jens Petersen⁴

¹Laboratory for Atmospheric and Space Physics, University of Colorado, Boulder, Colorado 80303, United States.

The Journal of Physical Chemistry. A

|June 15, 2026

Summary

This study investigates aziridine

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Area of Science:

Physical Chemistry
Chemical Physics
Spectroscopy

Background:

Aziridine is a nitrogen-bearing hydrocarbon with the chemical formula c-C2H4NH.
Understanding its electronic structure and decomposition pathways is crucial for various chemical applications.

Purpose of the Study:

To investigate the threshold photoelectron spectrum, dissociative photoionization, and pyrolysis of aziridine.
To determine the adiabatic ionization energy (AIE) of aziridine and its isomers.
To elucidate the fragmentation patterns and isomerization mechanisms of aziridine under different conditions.

Main Methods:

Double-imaging photoelectron photoion coincidence spectroscopy at the Swiss Light Source.
Simulation of the threshold photoelectron spectrum using the Thawed Gaussian Approximation (TGA) method.
Statistical modeling to determine appearance energies for dissociative ionization.

Main Results:

The adiabatic ionization energy (AIE) of aziridine was measured at (9.30 ± 0.03) eV.
Dissociative photoionization yielding hydrogen loss and methyl loss occurred at (10.59 ± 0.05) eV and (10.53 ± 0.05) eV, respectively.
Aziridine pyrolysis at 1360 K produced ethenamine, methyl radical, and H2CN• radicals, with ethenamine's AIE measured at (8.16 ± 0.03) eV.

Conclusions:

Isomerization plays a significant role in the thermal decomposition of neutral aziridine.
Multiple C2H5N isomers contribute to aziridine's thermal decomposition pathways.
The study provides detailed insights into the electronic properties and fragmentation dynamics of aziridine and its related isomers.