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Cesium's Off‐the‐Map Valence Orbital
Author(s) -
Goesten Maarten G.,
Rahm Martin,
Bickelhaupt F. Matthias,
Hensen Emiel J. M.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704118
Subject(s) - hypervalent molecule , chemistry , valence (chemistry) , atomic orbital , non bonding orbital , molecular orbital , atomic physics , caesium , molecular orbital theory , ion , rydberg formula , crystallography , electron , molecular physics , physics , molecule , ionization , inorganic chemistry , quantum mechanics , organic chemistry , reagent
The T d ‐symmetric [CsO 4 ] + 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 XeO 4 : 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.