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Cesium's Off-the-Map Valence Orbital.

ABSTRACT: The T_d -symmetric [CsO₄ ]⁺ ion, featuring Cs in an oxidation state of 9, is computed to be a minimum. Cs uses outer core 5s and 5p orbitals to bind the oxygen atoms. The valence Cs 6s orbital lies too high to be involved in bonding, and contributes to Rydberg levels only. From a molecular orbital perspective, the bonding scheme is reminiscent of XeO₄ : an octet of electrons to bind electronegative ligands, and no low-lying acceptor orbitals on the central atom. In this sense, Cs⁺ resembles hypervalent Xe.

SUBMITTER: Goesten MG

PROVIDER: S-EPMC5601296 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Cesium's Off-the-Map Valence Orbital.

Goesten Maarten G MG Rahm Martin M Bickelhaupt F Matthias FM Hensen Emiel J M EJM

Angewandte Chemie (International ed. in English) 20170718 33

The Td -symmetric [CsO4 ]+ ion, featuring Cs in an oxidation state of 9, is computed to be a minimum. Cs uses outer core 5s and 5p orbitals to bind the oxygen atoms. The valence Cs 6s orbital lies too high to be involved in bonding, and contributes to Rydberg levels only. From a molecular orbital perspective, the bonding scheme is reminiscent of XeO4 : an octet of electrons to bind electronegative ligands, and no low-lying acceptor orbitals on the cent ...[more]

PMID: 28643352

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