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Theoretical study on the Br + CH3SCH3 reaction
Hui Zhang1, Gui-Ling Zhang, Li Wang
1College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, People's Republic of China.
Bromine atom reactions with dimethyl sulfide (CH(3)SCH(3)) were studied. Hydrogen abstraction is the dominant pathway, aligning with experimental data and providing a rate constant expression for this important chemical process.
Area of Science:
- Chemical Kinetics
- Theoretical Chemistry
- Reaction Dynamics
Background:
- Dimethyl sulfide (CH(3)SCH(3)) is a significant atmospheric sulfur compound.
- Understanding bromine atom reactions is crucial for atmospheric chemistry and combustion processes.
Purpose of the Study:
- Investigate the reaction mechanism and kinetics of bromine atom with dimethyl sulfide.
- Determine the rate constants for individual reaction channels.
- Provide a theoretical basis for experimental observations.
Main Methods:
- Direct dynamics method employed for theoretical investigation.
- High-level computational chemistry methods (MP2/6-31+G(d,p) and G3(MP2)) used for electronic structure calculations.
- Canonical variational transition state theory with small-curvature tunneling correction applied for rate constant calculations.
Main Results:
- Optimized geometries, frequencies, and minimum energy paths were determined.
- Rate constants for three reaction channels (hydrogen abstraction, CH(3)SBr formation, CH(3)S formation) were calculated over 200-3000 K.
- Total rate constants show good agreement with experimental data, yielding the expression k(T) = 2.68 x 10(-12) exp(-1235.24/T) cm(3)/(molecule s).
Conclusions:
- Hydrogen abstraction (Br + CH(3)SCH(3) --> CH(3)SCH(2) + HBr) is the predominant reaction pathway.
- The other two channels are minor contributors across the studied temperature range.
- The theoretical model accurately predicts the overall reaction kinetics, validating its applicability to similar systems.
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