Abstract
The Born-Oppenheimer electronically adiabatic basis provides the most convenient representation for obtaining molecular-structure and potential-energy-surface information for systems of chemical interest. In this representation the electronic Hamiltonian is diagonal, and the adiabatic energies may be defined and calculated accurately by the variational principle. For systems in which the adiabatic states are well separated in energy, the nuclear motion at chemical energies can be treated adequately using a single adiabatic potential energy surface. For systems in which the coupling of electronic states is important, the coupling can be included consistently in this representation through matrix elements of nuclear-motion derivative operators.
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Garrett, B.C., Truhlar, D.G., Melius, C.F. (1983). Derivative Coupling Elements in Electronically Adiabatic Representations and Their Use in Scattering Calculations. In: Hinze, J. (eds) Energy Storage and Redistribution in Molecules. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-3667-9_22
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DOI: https://doi.org/10.1007/978-1-4613-3667-9_22
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