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Chemistry · Glossary

What is Born–Oppenheimer approximation?

Also known as: Born--Oppenheimer approximation

Definition 3.1 University Chemistry — Year 3 · Chapter 3 — Computational Chemistry: Hartree–Fock and DFT

In the Born–Oppenheimer approximation, the electronic Schrödinger equation is solved for nuclei held fixed at positions R\mathbf R,

H^el ψel(r;R)=Eel(R) ψel(r;R),\hat H_{\mathrm{el}}\,\psi_{\mathrm{el}}(\mathbf r;\mathbf R) = E_{\mathrm{el}}(\mathbf R)\,\psi_{\mathrm{el}}(\mathbf r;\mathbf R),

and the nuclei then move in the potential Eel(R)+Vnn(R)E_{\mathrm{el}}(\mathbf R) + V_{\mathrm{nn}}(\mathbf R), the electronic energy plus the repulsion of the nuclei.

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