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NO (A) Rotational State Distributions from Photodissociation of the N2-NO Complex
Bradley F Parsons1, Marcos R Rivera1, Michael K Onder1
1Department of Chemistry and Biochemistry, Creighton University, 2500 California Plaza, Omaha, Nebraska 68178, United States.
Photodissociation of the N2-NO complex reveals surprising rotational energy distributions in the resulting nitrogen oxide (NO) and nitrogen (N2) products. The NO fragment exhibits a colder-than-expected rotational state distribution, with N2 rotating more energetically.
Area of Science:
- Chemical Physics
- Molecular Spectroscopy
- Photochemistry
Background:
- The N2-NO complex is a key system for studying energy transfer during molecular photodissociation.
- Understanding the partitioning of energy into product rotation and translation is crucial for reaction dynamics.
Purpose of the Study:
- To investigate the rotational state distributions of NO (A) products from N2-NO complex photodissociation.
- To determine the energy disposal into rotational and translational modes of the fragments.
Main Methods:
- Resonance-enhanced multiphoton ionization (REMPI) spectroscopy was used to probe NO (A) products.
- Measurements were conducted at various excitation energies above the dissociation threshold.
- Rotational state distributions were analyzed to infer energy partitioning.
Main Results:
- NO (A) rotational states exceeding available energy were observed at low excitation, attributed to complex hotbands.
- At higher energies, observed NO (A) rotational states were energetically allowed but typically biased towards low rotational levels.
- The average fraction of energy in NO (A) rotation (f_NO rot,ave) was determined to be 0.088 at the highest energy, increasing with decreasing available energy.
- The N2 fragment was found to possess higher average rotational energy than the NO fragment.
Conclusions:
- The NO (A) rotational state distribution is colder than predicted by statistical dissociation models.
- Energy partitioning favors translation and N2 rotation over NO rotation.
- These findings provide insights into the dynamics of N2-NO complex photodissociation.
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