Where does the dimethyl ether internal rotation barrier come from?

Lionel Goodman, Vojislava Pophristic

Research output: Contribution to journalArticlepeer-review

35 Scopus citations


The energetic consequences of skeletal relaxation and natural bond orbital and symmetry decomposition of the barrier energy for dimethyl ether internal rotation is analysed. The largest contribution to the barrier energy is found to involve increased p character in the oxygen σ lone-pair on going to the barrier top. Opening of the COC angle, occurring because of increased Pauli exchange repulsion between in-plane C-H methyl orbitals is responsible for the p character increase. However, the Pauli repulsion does not contribute importantly to the barrier energy. π-interaction effects are found to give important, but not dominant barrier energy contributions.

Original languageEnglish (US)
Pages (from-to)287-295
Number of pages9
JournalChemical Physics Letters
Issue number3-4
StatePublished - Sep 6 1996
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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