Superhalogens. Halogen atoms possess the highest EAs (3.0-3.6 eV) among all the atoms, however, molecules may exceed the 3.6 eV limit due to collective effects. There is a class of molecules, known as superhalogens [1] that are especially important oxidizers. In 1981 we proposed a simple formula for one class of superhalogens, MXk+1, where M is a main group or transition metal atom, X is a halogen atom, and k is the maximal formal valence of the atom M [1]. Molecules with high electron affinities (EAs) play a very important role in chemistry. For example, in 1962, Bartlett synthesized the first chemically bound xenon in Xe+[PtF6]- [2]. This milestone work started the Chemistry of Nobel Gases, which previously have been considered as absolutely inert atoms.2 While superhalogen anions are well characterized in condensed phases, their gas-phase electron detachment energies (EDE) have not yet been measured experimentally. Only recently, the first photoelectron spectra of the MX2- (M = Li, Na; X = Cl, Br, I) superhalogen anions have been obtained by. L.-S. Wang and co-workers [3]. The first vertical detachment energies (VDEs) were measured to be 5.92±0.04 eV (LiCl2-), 5.86±0.06 eV (NaCl2-), 5.42±0.03 eV (LiBr2-), 5.36±0.06 eV (NaBr2-), 4.88±0.03 eV (LiI2-), and 4.84±0.06 eV (NaI2-), which are all well above the 3.61 eV EDE of Cl-, the highest among atomic anions. The highest VDE was found for LiCl2-: VIP=5.92±0.04 eV. The highest electron affinity probed by photoelectron spectroscopy was found for ZrF5-: VDE>7.5 eV [4]. We plan to work in close collaborations with L.-S. Wang in further search for superhalogens with record high EDE, which will be exceptionally strong oxidizers.
- DVM-Xa Calculations on the Ionization Potentials of [MXk+1]- Complex Anions and the Electron Affinities of MXk+1 "Superhalogens". G. L. Gutsev and A. I. Boldyrev. Chem. Phys., 56, 277 (1981).
- Xenon Hexafluoroplatinate (V) Xe+[PtF6]-. N. Bartlett, Proc. Chem. Soc. 218 (1962).
- First Experimental Photoelectron Spectra of Superhalogens and Their Theoretical Interpretations. X.-B. Wang, C.-F. Ding, L. S. Wang, A. I. Boldyrev and J. Simons, J. Chem. Phys., 110, 4763 (1999).
- Experimental Observation of a Very High Second Electron Affinity for ZrF6 from Photodetachment of Geseous ZrF62- Doubly Charged Anions. X.-B. Wang, L. S. Wang, J. Phys. Chem. A, 104, 4429 (2000).
Complete list of our publications on superhalogens:
36. First Experimental Photoelectron Spectra of Superhalogens and Their Theoretical Interpretations. X.-B. Wang, C.-F. Ding, L. S. Wang, A. I. Boldyrev and J. Simons. J. Chem. Phys., 110, 4763 (1999).
35. Adiabatic Electron Affinities of Small Superhalogens: LiF2, LiCl2, NaF2, and NaCl2. G. L. Gutsev, R Bartlett, A. I. Boldyrev and J. Simons. J. Chem. Phys., 107, 3867 (1997).
34. Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluoromettalates MF63-, M=Sc, Y, La, ZrF62-, and TaF6-.
M. Gutowski, A. I. Boldyrev, J. Simons, J. Rak and J. Blazejowski.
J. Am. Chem. Soc., 118, 1173 (1996).
170. Small Mutiply Charged Anions as Building Blocks in Chemistry. (Review). A. I. Boldyrev, M. Gutowski and J. Simons. Acc. Chem. Res., 29, 497 (1996).
33. Vertical Electron Detachment Energies for Octahedral Closed-Shell Multiply Charged Anions. M. Gutowski, A. I. Boldyrev, J. V. Ortiz, J. Simons. J. Am. Chem. Soc. 116, 9262 (1994).
32. Vertical and Adiabatic Ionization Potentials of MHk+1- Anions. Ab initio Study of the Structure and Stability of Hypervalent MHk+1 molecules. A. I. Boldyrev and J. Simons. J. Chem. Phys. 99, 4628 (1993).
31. Is TeF82- the MXn2- Dianon with the Largest Electron Detachment Energy (5 eV)? A. I. Boldyrev and J. Simons. J. Chem. Phys., 97, 2826 (1992).
30. The First Ionization Potentials of Some MHk+1- and M2H2k+1- Anions Calculated by a Green's Function Method. A. I. Boldyrev and W. von Niessen. Chem. Phys., 155, 71 (1991).
29. On the Existence of Free Doubly Negative Molecular Ions.
H.-G. Weikert, L. S. Cederbaum, F. Tarantelli and A. I. Boldyrev.
Zeitschrift fur Physik D, 18, 299 (1991).
28. Ab initio Study of Structure, Stability and Ionization Potentials of the Anions PF6- and P2F11-. C. Kolmel, G. Palm, R. Ahlrichs, M. Bar and A. I. Boldyrev. Chem. Phys. Lett., 173, 151 (1990).
27. The Upper Ionization Potentials of F-, LiF2-, BeF3-, BO2-, AlO2- and NO3- Ions Calculated by Green's Function Methods. V. G. Zakrzewski and A. I. Boldyrev. J. Chem. Phys., 93, 657 (1990).
26. The First Ionization Potentials of Anions, Calculated by the Green's Function Methods. V. G. Zakzhevskii and A. I. Boldyrev. Zh. Neorg. Khim. (Russ.) 35, 711 (1990).
25. Theoretical Estimation of the Maximal Value of the First,
Second and Higher Electron Affinity of Chemical Compounds.
G. L. Gutsev and A. I. Boldyrev. J. Phys. Chem., 93, 2256 (1990).
24. The Problem of the Second and More Higher Electron Affinities of the Chemical Compounds. G. L. Gutsev and A. I. Boldyrev
Izv. AN SSSR, Ser. Khim. (Russ.) N7, 1679 (1989).
23. The Relationship Between Geometrical and Electronic Structures in Transition Metal Tetrafluorides. G. L. Gutsev and A. I. Boldyrev. Int. J. Mass Spectrom. and Ion Processes, 91, 135 (1989).
22. A Theoretical Estimate of the Maximum Value of the Electron Affinity of Chemical Compounds. G. L. Gutsev and A. I. Boldyrev. Zh. Fiz. Khim. (Russ.) 63, 2116 (1989).
21. The Role of Electron Correlation in the estimation of the Electron Affinity of Superhalogens. V. G. Zakzhevskii and A. I. Boldyrev.
Zh. Neorg. Khim. (Russ.) 34, 1368 (1989).
20. The Relationship Between the Geometric Structure and the Electronic Structure in Transition Metal Tetrafluorides. G. L. Gutsev and A. I. Boldyrev. Zh. Neorg. Khim. (Russ.) 34, 304 (1989).
19. Theoretical Calculation of the Electron Affinity of the I3 Radical
G. L. Gutsev, A. I. Boldyrev and A. A. Ovchinnikov. Zh. Fiz. Khim. (Russ.) 62, 383 (1988).
18. Theoretical Calculation of the Electron Affinity of the Pentafluorides of the Group V Elements. G. L. Gutsev, A. I. Boldyrev and A. A. Ovchinnikov. Zh. Fiz. Khim. (Russ.) 62, 378 (1988).
17. An Explanation of the Lower Stability of MFk+1 Radicals Compared with MFk+1- Anions. G. L. Gutsev and A. I. Boldyrev. Zh. Neorg. Khim. (Russ.) 32, 1535 (1987).
16. The Electronic Structure of Superhalogens and Superalkalies. (Review).
G. L. Gutsev and A. I. Boldyrev. Usp. Khim. (Russ.) 51, 889 (1987).
15. The Theoretical Investigation of the Electron Affinity of Chemical Compounds. (Review). G. L. Gutsev and A. I. Boldyrev. Adv. Chem. Phys., 61, 169 (1985).
14. Electronic Structure of the Hexafluorides of the 3d- and 4d- Metals.
G. L. Gutsev and A. I. Boldyrev. Koord. Khim. (Russ.) 11, 435 (1985).
13. Electronic Structure of the UO2F53- Anion Calculated by DVM-Xa Method. V. I. Sergeenko, L. N. Ignatjeva, G. L. Gutsev and A. I. Boldyrev. Zh. Strukt. Khim. (Russ.) v.26, N1, 131 (1985).
12. Explanation of the Trend of Electron Affinities of the Tetraoxides of the 3d- and 4d-metals. G. L. Gutsev and A. I. Boldyrev. Zh. Strukt. Khim. (Russ.) v.26, N1, 22 (1985).
11. The Search of the Systems with the Maximal Electron Affinity.
G. L. Gutsev and A. I. Boldyrev. Zh. Strukt. Khim. (Russ.) v.25, N5, 16 (1984).
10. Electronic Structure of the Negative Hexafluorides of the 3d-metals.
G. L. Gutsev and A. I. Boldyrev. Koord. Khim. (Russ.) 10, 1455 (1984).
9. The Electronic Structure of the 3d- and 4d-metal Hexafluoride Anions and the Electron Affinities of the Corresponding Neutrals.
G. L. Gutsev and A. I. Boldyrev. Mol. Phys., 53, 23 (1984).
8. The Relationship Between the Electronic Structures of the 3d and 4d Metal Tetraoxianions and the Electron Affinities of the Corresponding Neutrals. G. L. Gutsev and A. I. Boldyrev.
Chem. Phys. Lett., 108, 255 (1984).
7. The Way to Systems with the Highest Possible Electron Affinity.
G. L. Gutsev and A. I. Boldyrev. Chem. Phys. Lett., 108, 250 (1984).
6. An Explanation of the High Electron Affinities of the 5d-Metal Hexafluorides. G. L. Gutsev and A. I. Boldyrev.
Chem. Phys. Lett., 101, 441 (1983).
5. DVM-Xa Calculations of the Electronic Structure of [MClk+1]- Complex Chloro-Anions. G. L. Gutsev and A. I. Boldyrev.
Zh. Neorg. Khim. (Russ.) 27, 868 (1982).
4. DVM-Xa Calculations on the Electronic Structure of Complex Chlorine Anions. G. L. Gutsev and A. I. Boldyrev. Chem. Phys. Lett., 84, 352 (1981).
3. Connection between the Electron Affinity of MXk+1 Radicals and Their Electronic Structure. G. L. Gutsev and A. I. Boldyrev.
Zh. Neorg. Khim. (Russ.) 26, 2557 (1981).
2. DVM-Xa Calculations of the Electronic Structure of the Anionic Complexes MXk+1. G. L. Gutsev and A. I. Boldyrev. Zh. Neorg. Khim. (Russ.) 26, 2353 (1981).
1. DVM-Xa Calculations on the Ionization Potentials of [MXk+1]- Complex Anions and the Electron Affinities of MXk+1 "Superhalogens". G. L. Gutsev and A. I. Boldyrev. Chem. Phys., 56, 277 (1981).
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