The Diagonal Born-Oppenheimer Correction to Molecular Dynamical Properties

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We examine the effect of the diagonal Born–Oppenheimer correction on dynamics in two simple systems – the Hooke's atom in an external harmonic potential and the collinear hydrogen exchange reaction. The transmission probability for the Hooke's atom, calculated within the Born–Oppenheimer approximation, is simply shifted in energy with respect to the exact result, and this is corrected by the diagonal adiabatic contribution. The reaction probability for the H3 system reflects the fact, that the diagonal Born–Oppenheimer correction raises the barrier to the reaction by approximately 70 cm−1.


NOTICE: this is the author’s version of a work that was accepted for publication in . Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in CHEMICAL PHYSICS LETTERS, [VOL#333, ISSUE#6, (JANUARY 26 2001)] DOI#10.1016/S0009-2614(00)01297-5

Garashchuk,S., Light,J.C. & Rassolov,V.A.(2001). The diagonal Born-Oppenheimer correction to molecular dynamical properties. Chemical Physics Letters, 333(6), 459-464.