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NOO Peroxy Isomer Exposed with Velocity-Map Imaging.
B A Laws1, S J Cavanagh1, B R Lewis1
1Research School of Physics and Engineering, The Australian National University , Canberra ACT 2601, Australia.
The Journal of Physical Chemistry Letters
|August 31, 2017
Summary
Researchers have identified the stable peroxy isomer of nitrogen dioxide (NOO), a key atmospheric gas. This discovery, using photoelectron spectroscopy, confirms the existence of this reactive species.
Area of Science:
- Atmospheric Chemistry
- Chemical Physics
- Spectroscopy
Background:
- Nitrogen dioxide (NO2) chemistry is typically understood via the ONO isomer.
- The peroxy isomer (NOO) has been theorized but not experimentally confirmed as stable.
- Understanding NO2 isomers is crucial for atmospheric trace gas studies.
Purpose of the Study:
- To experimentally confirm the existence and stability of the peroxy isomer of nitrogen dioxide (NOO).
- To characterize the electronic and vibrational properties of the NOO isomer.
- To provide new insights into the atmospheric chemistry of nitrogen oxides.
Main Methods:
- Velocity-map-imaged photoelectron spectroscopy of the nitrite anion (NO2-).
- Ab initio quantum chemical calculations.
- Analysis of energetic-electron structure and spectral data.
Main Results:
- Photoelectron spectra revealed distinct structures attributable to the NOO- isomer.
- The electron affinity of NOO was determined to be 335(30) cm-1.
- Vibrational frequencies for the NOO (X̃2A') ground state were established.
- Ab initio calculations supported the experimental findings.
Conclusions:
- The study provides the first direct experimental evidence for the stable peroxy isomer of nitrogen dioxide (NOO).
- The determined properties confirm NOO as an important, albeit previously unobserved, reactive species in atmospheric chemistry.
- This work opens new avenues for studying the reactivity and role of NOO in atmospheric processes.
