Mode-Selective Laser Control of Palladium Catalyst Decomposition

It is generally assumed that molecules behave ergodically during chemical reactions, that is, reactivities depend only on the total energy content and not on the initial state of the molecule. While there are a few examples of nonergodic behavior in small (usually electronically excited) species, to...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2018-01, Vol.9 (1), p.157-162
Main Authors: Carr, Patrick J. J, Lecours, Michael J, Burt, Michael J, Marta, Rick A, Steinmetz, Vincent, Fillion, Eric, Hopkins, W. Scott
Format: Article
Language:English
Subjects:
Chemical Physics
Physics
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Summary:It is generally assumed that molecules behave ergodically during chemical reactions, that is, reactivities depend only on the total energy content and not on the initial state of the molecule. While there are a few examples of nonergodic behavior in small (usually electronically excited) species, to date there have been no reports of such behavior in larger covalently bound species composed of several tens of atoms. Here, we demonstrate vibrational mode-selective behavior in a series of palladium catalysts. When we excite solvent-tagged gas-phase Pd catalysts with an infrared laser that is tuned to be resonant with specific molecular vibrations, depending on which vibration we excite, we can select different reaction pathways. We also demonstrate that this behavior can be “turned off” via chemical substitution.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.7b03030