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Following an overview on the nature of bonding of such hypervalent molecules as LinA (Li6C, Li30, Li40, Li3S, Li4S, Li4P) and M2CN (M=Li, Na, K), the present paper deals with the molecular and electronic structures of newly found lithium-rich Li2F and Li2OH molecules as well as Li2Fn-1 (n= 3, 4) and Lin(OH)n-1(n=3-5) clusters which have been detected in supersonic beams effusing from a laser ablation source. The ionization energies (IEs) determined by photoionization were 3.78 •} 0.2 eV for Li2F, 4.32 •} 0.2 eV for Li3F2, and 4.30 •} 0.2 eV for Li4F3. Agreements of thhse IEs with theoretical ones calculated by ab initio MO methods support that Li2F is in a hyperlithiated configuration (HLC) in which the excess electron delocalizes over the two lithiums, while Li3F2 and Li4F3 are in a segregated configuration (SC) comprising ionic and non-ionic lithiums resulting from localization of the excess valence electron. Ionization efficiency curves (IECs) measured for Lin(OH)n_1(n=2-5) are well reproduced with a simulation involving Franck-Condon factors, and this enabled us to identify the global-minimum structure of these species predicted by theoretical calculations with the DFT method. The IEs determined were 4.053 •} 0.003 eV for Li20H in HLC, 3.687 •} 0.003 eV for Li3(OH)2 in HLC, 4.133 •} 0.003 eV for Li3(OH)2 in SC, and 3.418 •} 0.009 eV for Li4(OH)3 in SC, and 3.60 •} 0.11 eV for Li5(OH)4 in SC. Also, IE of Li30 was determined as 3.59 •} 0.02 eV from reinvestigation with the photoionization technique. Furthermore, Li3O was found to be a floppy molecule sharing both the D3h and C2v structures from a precise analysis of the observed IEC taking account of the potential energy surface for both neutral and cationic Li3O. This is the first experimental evidence for "electronomers" or electronic isomers of Li3O, which have nearly the same stability but are different in localization of the SOMO. It is eventually stressed that delocalization of the excess valence electron over all of the lithium atoms in a molecule is essential to afford hyperlithiated molecules and that the shape of SOMO or HOMO, which accommodates the excess valence electron or electrons, plays a key role in determining the stability of hyperlithiated molecules.

The Nature of Bonding of Hyperlithiated Molecules Beyond the Octet Rule