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<p>A recent paper in this journal has argued strongly in favour of the view that going beyond the Born-Oppenheimer approximation in quantum chemistry offers an explanation of chemical facts by quantum theory. In essence the claim amounts to believing that any molecule’s chemistry can be accounted for in terms of the discrete energy levels of the Coulomb Hamiltonian for the collection of electrons and nuclei specified by the molecular formula without reference to the traditional Born-Oppenheimer arguments. This is ‘The Isolated Molecule’ model since only the internal interactions of the electrons and nuclei are considered. The Comment suggests that such an approach is only suitable for atoms and diatomic molecules since there is no potential energy surface defined, and diagonalization of the Coulomb Hamiltonian, <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10698_2025_9552_Article_IEq1.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">\({\textsf{H}}\)</EquationSource> </InlineEquation>, simply yields energy levels for the whole molecule. The associated eigenfunctions provide a basis for irreducible representations of the Galilean relativity group augmented by space-inversion and appropriate permutation groups (for identical particles). Some misquotations from the author’s work are corrected.</p>

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Comment on The Born-Oppenheimer approximation and its role in the reduction of chemistry

  • 期刊论文

  • 发表日期：

    2025年9月5日

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  • R. Guy Woolley

摘要

A recent paper in this journal has argued strongly in favour of the view that going beyond the Born-Oppenheimer approximation in quantum chemistry offers an explanation of chemical facts by quantum theory. In essence the claim amounts to believing that any molecule’s chemistry can be accounted for in terms of the discrete energy levels of the Coulomb Hamiltonian for the collection of electrons and nuclei specified by the molecular formula without reference to the traditional Born-Oppenheimer arguments. This is ‘The Isolated Molecule’ model since only the internal interactions of the electrons and nuclei are considered. The Comment suggests that such an approach is only suitable for atoms and diatomic molecules since there is no potential energy surface defined, and diagonalization of the Coulomb Hamiltonian, \({\textsf{H}}\) , simply yields energy levels for the whole molecule. The associated eigenfunctions provide a basis for irreducible representations of the Galilean relativity group augmented by space-inversion and appropriate permutation groups (for identical particles). Some misquotations from the author’s work are corrected.