Alkaline earth metal atoms electron transfer

Alkaline earth metal atoms have fairly low ionization potentials, as have alkali metal atoms (e.g., 5.21 and 5.14 eV for barium and sodium, respectively [89]). Hence the reactions of alkaline earth metal atoms with oxidizing molecules are also expected to be initiated by an electron transfer and should follow the harpoon mechanism. However, alkali metal atoms are monovalent species, whereas alkaline earth metal atoms have two valence electrons. Hence peculiarities are to be expected in the alkaline earth metal reaction dynamics, especially when doubly charged products such as BaO are to be formed [90]. The second valence electron also opens up the possibility of chemiluminescent reactions, which are largely absent in alkali metal atom reactions [91, 92]. The second electron causes the existence of low-lying excited states in the product. 

Dramatic effects of electronic excitation on the reaction mechanisms have been demonstrated in several cases. One of the first reported examples must be recalled here also as it falls outside the scope of this chapter. Electronically excited 0( D) is much more reactive than ground-state 0( P) and inserts into the C-H bonds of methane [162]. Similar state specificity in the reactivity has also been encountered in electron-transfer reactions and seems to be the rule in light systems. Its origin has been explored systematically in alkali and alkaline earth metal atom reactions. Before discussing some of the studies, it is appropriate to survey a much simpler situation where electronic excitation affects the dynamics of the reaction just by changing the location of the electron-transfer region. 

For a general formulation of the Zintl-Klemm concept, consider an intermetallic AmX phase, where A is the more electropositive element, t3 pically an alkali or an alkaline earth metal. Both A and X, viewed as individual atoms, are assumed to follow the octet rule leading to transfer of electrons from A to X, i.e., A AF, X —> X , so that mp = nq. The anionic unit X arising from this electron transfer is considered to be a pseudoatom, which exhibits a structural chemistry closely related to that of the isoelectronic elements [11]. Since bonding also is possible in the cationic units, the numbers of electrons involved in A-A and X-X bonds of various types (caa and exx> respectively) as well as the number of electrons e not involved in localized bonds can be generated from the numbers of valence electrons on A and X, namely and ex, respectively, by the following equations of balance ... 

The periodic system developed from Bohr s atomic theory is of the greatest importance in chemical science because it demonstrates that the properties of the elements depend on their positions in the system. It is immediately apparent that chemical valency depends on the number of loosely-bound electrons in the atom. Thus, the alkali metals have one such electron while the divalent alkaline-earth metals have two, etc. Valency is therefore closely connected with electronic structure and provides the foundation for the modern theory of the chemical bond, the basis of which is to be found in the coupling or transfer of the valency electrons. 

The alkali metals are the most chemically active metals. Alkaline earth metals are second in reactivity. Elements in the same family have the same outermost electron configuration. Alkali metals have one outermost electron that is easily transferred to needy atoms. Alkaline earth metals have two outermost electrons to share or transfer. The transition metals are the least active. 

Around 1928, Zintl had begun to investigate binary intermetallic compounds, in which one component is a rather electropositive element, e.g., an alkali- or an alkaline earth metal [1,2]. Zintl discovered that in cases for which the Hume-Rothery rules for metals do not hold, significant volume contractions are observed on compound formation, which can be traced back to contractions of the electropositive atoms [2]. He explained this by an electron transfer from the electropositive to the electronegative atoms. For example, the structure of NaTl [3] can easily be understood using the ionic formulation Na Tl" where the poly- or Zintl anion [TF] forms a diamond-like partial structure - one of the preferred structures, for a four electron species [1,2], Zintl has defined a class of compounds, which, in the beginning, was a somewhat curious link between well-known valence compounds and somehow odd intermetallic phases. 

Components of Zintl phases are metals A (Li-Cs, Mg-Ba) and semimetals X (B-Tl, Si-Pb, P-Bi, Te). The definition of the components of Zintl phases is not quite sharp, neither for the metals nor for the semimetals, until today. While the alkali- and alkaline earth metals are undoubtedly metals in the classical sense, there is still the vast field of transition metals T, which in Zintl type compoimds, might also occur. Electropositive T atoms may replace the main group metal A and electronegative ones tike a semimetal X. One of the wellknown examples here is CsAu (a diamagnetic semiconductor). This phase shows the typical properties of a valence compound according to the electron transfer description Cs Au [4]. 

The skeletal bonding of the individual polyhedra is then investigated leading to determination of their MO energy parameters. (3) Electrons are transferred from the more electropositive element, typically an alkali metal, an alkaline-earth metal, or a lanthanide, to the boron framework until the bonding orbitals are filled. (4) Excess valence electrons on the metal atoms are regarded as metallic and presumed to lead to metallic optical and electrical properties. 

Among the alkali metals, Li, Na, K, Rb, and Cs and their alloys have been used as exohedral dopants for Cgo [25, 26], with one electron typically transferred per alkali metal dopant. Although the metal atom diffusion rates appear to be considerably lower, some success has also been achieved with the intercalation of alkaline earth dopants, such as Ca, Sr, and Ba [27, 28, 29], where two electrons per metal atom M are transferred to the Cgo molecules for low concentrations of metal atoms, and less than two electrons per alkaline earth ion for high metal atom concentrations. Since the alkaline earth ions are smaller than the corresponding alkali metals in the same row of the periodic table, the crystal structures formed with alkaline earth doping are often different from those for the alkali metal dopants. Except for the alkali metal and alkaline earth intercalation compounds, few intercalation compounds have been investigated for their physical properties. 

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