Electronic and nuclear separation in molecules
The Born–Oppenheimer approximation separates electronic and nuclear motion by solving an electronic problem at fixed nuclear geometry and then describing nuclear motion on the resulting energy surface.
Key knowledge
The Born–Oppenheimer approximation separates electronic and nuclear motion by solving an electronic problem at fixed nuclear geometry and then describing nuclear motion on the resulting energy surface. The large nuclear/electronic mass contrast motivates this separation, but coupling between electronic states can invalidate it.
Conditions and scope
- Near electronic degeneracies and strong nonadiabatic coupling, one isolated electronic surface may be insufficient.
- A molecular potential surface is a model-derived quantity and depends on the electronic approximation.
Sources · 1
References
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Evidence and review
Inspected IUPAC wavefunction factorization and degeneracy limitation.
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Entry details
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- uni-chem-born-oppenheimer
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- core.1
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- University core expansion