title: Nature of the chemical bond in transition: dissection of radical-molecule reactivity.
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.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: Heather A
authors.initials: HA
authors.lastname: Rypkema
authors.forename: Neil M
authors.initials: NM
authors.lastname: Donahue
authors.forename: James G
authors.initials: JG
authors.lastname: Anderson