Determining Transition-State Geometries in Liquids Using 2D-IR

Many properties of chemical reactions are determined by the transition state connecting reactant and product, yet it is difficult to directly obtain any information about these short-lived structures in liquids. We show that two-dimensional infrared (2D-IR) spectroscopy can provide direct informatio...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2008-03, Vol.319 (5871), p.1820-1823
Main Authors: Cahoon, James F, Sawyer, Karma R, Schlegel, Jacob P, Harris, Charles B
Format: Article
Language:English
Subjects:
Chemical reactions
Chemistry
Energy
Energy transfer
Exact sciences and technology
General and physical chemistry
Geometry
Infrared radiation
Ligands
Molecules
Research methodology
Spectroscopy
Spectrum analysis
Theory of reactions, general kinetics
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
Time constants
Vibration mode
Vibrational spectra
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Summary:Many properties of chemical reactions are determined by the transition state connecting reactant and product, yet it is difficult to directly obtain any information about these short-lived structures in liquids. We show that two-dimensional infrared (2D-IR) spectroscopy can provide direct information about transition states by tracking the transformation of vibrational modes as a molecule crossed a transition state. We successfully monitored a simple chemical reaction, the fluxional rearrangement of Fe(CO)â‚…, in which the exchange of axial and equatorial CO ligands causes an exchange of vibrational energy between the normal modes of the molecule. This energy transfer provides direct evidence regarding the time scale, transition state, and mechanism of the reaction.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.1154041