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Updated: May 24, 2026

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
Published on: April 15, 2013
Nature of the chemical bond in transition: dissection of radical-molecule reactivity
Heather A Rypkema1, Neil M Donahue, James G Anderson
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
Abstract:
A complete method for quantifying the Born-Oppenheimer barriers of radical--molecule abstraction reactions is derived from first principles with the dual objectives of analytical prediction and conceptual understanding. Expanding upon the work of Donahue et al. (J. Phys. Chem. A 1998, 102, 3923-3933) this treatment uses the strategic construction of reactant-like and product-like wave functions to evaluate the coupling between crossing diabatic states. The overall reaction coordinate is evaluated in a modular fashion, whereby each region is analyzed within the context of its governing physics.
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