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Search for Br* production in the D+DBr reaction
Jianyang Zhang1, Justin Jankunas, Nate C-M Bartlett
1Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
Photodissociation of deuterium bromide (DBr) yields deuterium atoms (D) that react with DBr. This reaction primarily forms ground-state bromine atoms, with the nonadiabatic channel producing excited bromine atoms contributing minimally.
Area of Science:
- Chemical Physics
- Molecular Dynamics
- Reaction Kinetics
Background:
- Deuterium bromide (DBr) photodissociation is a key process for studying atom-molecule reactions.
- Understanding reaction channels, including adiabatic and nonadiabatic pathways, is crucial for chemical dynamics.
- Spin-orbit coupling in bromine atoms influences reaction outcomes.
Purpose of the Study:
- To investigate the reaction dynamics of deuterium atoms (D) with deuterium bromide (DBr).
- To determine the branching ratios between adiabatic and nonadiabatic reaction channels.
- To quantify the contribution of spin-orbit excited bromine atoms (Br*) to the D+DBr reaction.
Main Methods:
- Pulsed jet expansion of DBr into a vacuum.
- Synchronized pulsed laser photodissociation of DBr.
- Detection of product molecular deuterium (D2) via ion imaging.
- Analysis of D2 product quantum states (vibrational and rotational) and collision energies.
Main Results:
- Photodissociation of DBr produces primarily ground-state bromine atoms ((2)P(3/2)) and fast D atoms.
- The D+DBr reaction proceeds through adiabatic (D2+Br) and nonadiabatic (D2+Br*) channels.
- The nonadiabatic channel, producing spin-orbit excited Br*, contributes 1% or less to the overall reaction under the studied conditions.
- Product D2 was observed in specific vibrational and rotational states (e.g., v'=1, J'=16-21; v'=2, J'=6-16; v'=3, J'=2-5).
Conclusions:
- The D+DBr reaction is dominated by the adiabatic pathway leading to ground-state bromine atoms.
- The spin-orbit splitting of bromine significantly influences the nonadiabatic reaction channel, making it a minor pathway.
- State-resolved ion imaging provides detailed insights into the dynamics of this important chemical reaction.
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