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2 Rational Design of Superatoms Using Electron‐Counting Rules
Puru Jena1, Hong Fang1, and Qiang Sun2,3
1 Physics Department, Virginia Commonwealth University, Richmond, Virginia, USA
2 School of Materials Science and Engineering, Peking University, Beijing, China
3 Center for Applied Physics and Technology, Peking University, Beijing, China
2.1 Introduction
The periodic table of elements developed by Mendeleev and presented at a meeting of the Russian Chemical Society on 6 March 1869, was based purely on the chemical properties of the then known elements. However, a fundamental understanding of the chemistry of the elements and the sites they occupy in the periodic table had to wait until the discovery of the electron in 1897 and the development of quantum mechanics in the early part of the twentieth century. Central to this understanding is the knowledge of the atomic orbitals and the manner in which they are filled as one moves along the columns and the rows of the periodic table. The elements belonging to the same column of the periodic table have similar chemistry. As one moves along the rows, the electrons continue to fill the successive atomic orbitals in keeping with the Pauli's principle and the chemistry changes accordingly. Consider, for example, the Group 18 elements, which have an outer electron configuration of ns 2 np 6. Because these orbitals are full, the energy cost to remove an electron is high and the energy gain in adding an electron is negligibly small. Thus, these elements do not participate in chemical reactions, justifying their name as the noble gas atoms. They are very stable and their bonding is characterized by weak van der Waals forces. The origin of their stability is, therefore, attributed to the electronic shell closure, which is referred to as the “octet rule” where 2 + 6 = 8 electrons are enough to fill the s and p orbitals. On the other hand, the group 1 alkali elements are characterized by an outer electron orbital occupation, namely ns 1. The energy cost to remove this electron, i.e., the ionization potential, is smaller than elements belonging to the same row in the periodic table and hence in a chemical reaction they tend to donate that electron, leaving behind an ionic core with closed electronic shells. Similarly, group 17 halogen atoms have an outer electron configuration of ns 2 np 5 and need an extra