Thus far, relationships between atomic radii and electronegativity have mostly been sought under ambient conditions and have been rationalized by comparing different atoms. Pitzer pointed out the periodic behavior in the two atomic properties long ago 30 and many others have relied on different definitions of atomic radii (usually covalent radii) and electrostatic relationships to define scales of electronegativity. The closer the electrons are to the nucleus, the more tightly they are bound, thus increasing the electronegativity of the atom. 22–29 and references therein).Ī relationship is intuitively expected between electronegativity and radius: the size of an atom is determined by the distribution of electrons around its nucleus. 3,18–21 Electronegativity is a similarly well-studied concept that can be defined in many ways (see, e.g., ref. 7–9 Today, a variety of definitions of atomic radii with well-known uses exists, including, e.g., ionic, 10–12 covalent, 6,13–17 and vdW radii. One early motivation for attaining atomic and ionic sizes was to help understand X-ray diffraction patterns in terms of crystal structures, 5,6 another to provide a rationalization for metallization. 1,2 The history of quantifying the sizes of atoms under ambient conditions includes a large body of work, extending over the last one and a half-centuries (for a non-exhaustive summary of this history see ref.
Introduction Atomic radii and electronegativity are often quintessential for how chemistry is rationalized. Here, we show how compression can reveal a long sought-after connection between two central chemical concepts – van-der-Waals (vdW) radii and electronegativity – and how these relate to the driving forces behind chemical and physical transformations. Trends in atomic properties are well-established tools for guiding the analysis and discovery of materials.
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