Superalkalies

Superalkalies. Alkali metal atoms possess the lowest ionization energies IEs (5.4-3.9 eV) among all the atoms, however, molecules may possess even lower IE then the 3.9 eV limit due to collective effects. There is a class of molecules, known as superalkalies [1]. In 1981 we have shown that species characterized by the formular MLk+1, where M is a main group or transition metal atom, L is an alkali metal atom, and k is the maximal formal valence of the atom M [1] possess lower IE then alkali metal atoms. Molecules with low IE may play an important role in chemistry. The low IE of superalkali species can be used in synthesis of new class of charge-transfer salts in which the corresponding anions are formed by the species with low electron affinity. The lowest experimentally measured electron detachment energy was found for Li3O: 3.54±0.30 eV [2], which is well below the 3.9 eV electron detachment energy of Cs, the lowest among atoms. We plan to work in further search for superalkalies with record low ionization energies, which will be exceptionally strong reducers.

1. DVM-Xa Calculations on the Electronic Structure of "Superalkali" Cations. G. L. Gutsev and A. I. Boldyrev. Chem. Phys. Lett., 92, 262 (1982).

2. Ionization Potentials of LinO (2<n<70) clusters: Experiment and Theory. P. Lievens, P. Thoen, S. Bouchaert, W. Bouwen, F. Vanhoutte, H. Weidele, R. E. Silverans, A. Navarro-Vazquez, and P. von R. Schleyer, J. Chem. Phys. 110, 10316 (1999).

Complete list of our publications on superalkalies:

8. Green Function Calculation of Ionization Energies of Hypermetallic Molecules. V. G. Zakrzewski, W. v. Niessen, A. I. Boldyrev and P. v. R. Schleyer. Chem. Phys. 174, 167 (1993).

7. Theoretical Search of the Large Rydberg Molecules: NH3CH3, NH2(CH3)2, NH(CH3)3 and N(CH3)4. A. I. Boldyrev and J. Simons. J. Chem. Phys. , 97, 6621 (1992).

6. Green Function Calculations of Ionization Energies of Hyperalkali Molecules. V. G. Zakrzewski, W. v. Niessen, A. I. Boldyrev and P. v. R. Schleyer. Chem Phys. Lett. 197, 195 (1992).

5. Ab initio Study Superalkalis. First Ionization Potentials and Thermodinamic Stability. E. Rehm, A. I. Boldyrev and P. v. R. Schleyer. Inorg, Chem. 31, 4834 (1992).

4. The Difference in the Electronic Structures of the Radicals MHk+1 and MLk+1 (L=Li, Na). G. L. Gutsev and A. I. Boldyrev. Zh. Neorg. Khim. (Russ.) 34, 1389 (1989).

3. The Electronic Structure of Superhalogens and Superalkalies. (Review).

G. L. Gutsev and A. I. Boldyrev. Usp. Khim. (Russ.) 51, 889 (1987).

2. The Difference in the Electronic Structures of the Radicals MHk+1 and MLk+1 (L=Li, Na). G. L. Gutsev and A. I. Boldyrev. Zh. Neorg. Khim. (Russ.) 34, 1389 (1989).

1. DVM-Xa Calculations on the Electronic Structure of "Superalkali" Cations. G. L. Gutsev and A. I. Boldyrev.

Chem. Phys. Lett., 92, 262 (1982).


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