Aggregation, molecular orbital modeling

Aggregates, controlling symmetry, 446 Aggregation, molecular orbital modeling, 457-470... 

Molecular Orbital Modeling of Monomeric Aggregates in Materials with Potentially Nonlinear Optical Properties... 

The dimer species, M2, was described by Huster (21) as a simple dissolved diatomic molecule. Such a species would be very unstable with respect to the ammoniated species, M + and e and may be ruled out by thermochemical data. The expanded metal dimer model of Becker, Lindquist, and Alder, in which two ammoniated metal ions are held together by a pair of electrons in a molecular orbital located principally between the two ions, is just as difficult to reconcile with optical, volumetric, and NMR data as the expanded metal monomer. In order to account for the similar absorption spectra of e, M, M2 (and any other species such as M or M4 that might exist at moderate concentrations of metal), Gold, Jolly, and Pitzer (16) assumed that species such as M and M2 consist of ionic aggregates in which the ammoniated electrons remain essentially unchanged from their state at infinite dilution. 

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