Inorganic Chemistry

This short essay seeks to identify and prevent a pitfall that attends less careful inquiries into “physiosemiosis.” It is emphasized that, in order to truly establish the presence of sign-action in the non-living world, all the components of a triadic sign - including the interpretant - would have to be abiotic (that is, not dependent on a living organism). Failure to heed this necessary condition can lead one to hastily confuse a natural sign (like smoke coming from fire) for an (...) instance of abiotic semiosis. A more rigorous and reserved approach to the topic is called for. (shrink)

At the heart of chemistry lies the periodic system of chemical elements. Despite being the cornerstone of modern chemistry, the overall structure of the periodic system has never been fully understood from an atomic physics point of view. Group-theoretical models have been proposed instead, but they suffer from several limitations. Among others, the identification of the correct symmetry group and its decomposition into subgroups has remained a problem to this day. In an effort to deepen our limited understanding of the (...) periodic law, we have extended the traditional Lie algebraic framework to account for the peculiar degeneracy structure of the periodic system. Starting from the four-dimensional hidden symmetry and accidental degeneracy of the hydrogen atom, as first revealed by Fock in 1935, our research has mainly focussed on the way this SO(4) symmetry of the Coulomb potential gets broken in the periodic system as a consequence of the transformation of the hydrogenic (n, l) filling order to the Madelung (n+l, n) order due to electronic repulsions, relativistic effects and spin-orbit couplings. In this PhD dissertation, a new left-step format of the periodic table is first proposed on the basis of the Madelung rule. Following the particle physics tradition, the chemical elements are then considered as various states of some 'atomic matter', which is described by a non-compact spectrum-generating dynamical Lie group. The chemical elements are shown to form a basis for a single infinite-dimensional degeneracy space of the SO(4,2) ⊗ SU(2) group. An explanation for the period doubling is then proposed in terms of a particular symmetry breaking of the SO(4,2) group to the anti de Sitter SO(3,2) group. The Madelung rule is rationalised on the basis of nonlinear Lie algebras which reflect the screening of the Coulomb hole. This opens new perspectives for a symmetry-based understanding of how the periodic law emerges from its quantum mechanical foundations, and holds the future promise of complementing our current phenomenological approach by a direct atomic physics approach. (shrink)

This chapter gives an overview of the evolution of the position of the rare-earth elements in the periodic system, from Mendeleev’s time to the present. Three fundamentally different accommodation methodologies have been proposed over the years. Mendeleev considered the rare-earth elements as homologues of the other elements. Other chemists looked upon the rare earths as forming a special intraperiodic group and therefore clustered the rare-earth elements in one of the groups of the periodic table. Still others adhered to the intergroup (...) accommodation of the rare earths, according to which the rare-earth elements do not show any relationship with the other elements, so that they had to be placed within the periodic table as a separate family of elements. The intergroup accommodation became the preferred one in the twentieth century. The advantages and disadvantages of the different representations of the modern periodic table are discussed. (shrink)