title: Entanglement in the Born-Oppenheimer Approximation.
abstract: The role of electron-nuclear entanglement on the validity of the Born-Oppenheimer (BO) approximation is investigated. Although nonadiabatic couplings generally lead to entanglement and to a failure of the BO approximation, surprisingly the degree of electron-nuclear entanglement is found to be uncorrelated with the degree of validity of the BO approximation. This is because while the degree of entanglement of BO states is determined by their deviation from the corresponding states in the crude BO approximation, the accuracy of the BO approximation is dictated, instead, by the deviation of the BO states from the exact electron-nuclear states. In fact, in the context of a minimal avoided crossing model, extreme cases are identified where an adequate BO state is seen to be maximally entangled, and where the BO approximation fails but the associated BO state remains approximately unentangled. Further, the BO states are found to not preserve the entanglement properties of the exact electron-nuclear eigenstates, and to be completely unentangled only in the limit in which the BO approximation becomes exact.
authors.affiliation: Department of Physical and Environmental Sciences, University of Toronto Scarborough , Toronto, Ontario M1C 1A4, Canada.|Chemical Physics Theory Group, Department of Chemistry, University of Toronto , Toronto, Ontario M5S 3H6, Canada.
authors.forename: Artur F
authors.identifier: 0000-0001-8035-6020
authors.initials: AF
authors.lastname: Izmaylov
authors.affiliation: Department of Chemistry and The Center for Coherence and Quantum Optics, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Ignacio
authors.initials: I
authors.lastname: Franco