Transcript ohio state.ppt

Vibrational Energy Disposal and Relative
Reactivity for the Vibrationally Driven Reaction
of CH3D with Cl in the C-H, C-D Combination
Region
Christopher J. Annesley
University of Wisconsin - Madison
How do vibrations affect reactions?
Local vs Normal modes
CH3D + Cl
CH3D(22 or 3+ 4) + Cl
S. Yoon, R. Holiday, and F. Crim, J. Chem. Phys. 119, 4755 (2003)
2ν2
ν3 + ν4
What we have seen
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Bond selective
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C-H Motions lead to C-H bond breakage
C-D Motions lead to C-D bond breakage
CH3D(1 or 4) + Cl
S. Yoon, R. Holiday, E. Sibert III, and F. Crim J. Chem. Phys. 119, 9568 (2003)
What we have seen
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Bond selective
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C-H Motions lead to C-H bond breakage
C-D Motions lead to C-D bond breakage
Mode Selective
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Different reactivities for different vibrations
CH3D() + Cl
R. Holiday, C. Kwon, C. Annesley and F. Crim J. Chem. Phys. 125, 133101 (2006)
CH3D(ν) + Cl
Spectator Model
What we have seen
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Bond selective
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Mode Selective
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C-H Motions lead to C-H bond breakage
C-D Motions lead to C-D bond breakage
Different reactivities for different vibrations
Spectator Model
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Multiple excited bonds lead to excited products
What should we look for in a new
system
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Multiple modes to compare
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Multiple excited bonds
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Spectators?
Different types of motions
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Mode selective
C-H vs C-D
|100>|1>
|100>|1>
A1
E
Infrared excitation cm-1
Products
Probe scan nm
Action Spectra
detecting ν2 CH2D
Infrared excitation cm-1
Action
Infrared excitation cm-1
PAD
Action Spectra
detecting ν1 CH3
Infrared excitation cm-1
Infrared excitation cm-1
Both action spectra
Infrared excitation cm-1
Summary
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Display of Spectator Model
Bond selective
Mode selective?
Thanks
F. Fleming Crim
F. Fleming Crim
Andrew Berke
Robert Holiday
Chan Ho Kwon
Funding: NSF